St. Catherine University SOPHIA 2015 Sr. Seraphim Gibbons Undergraduate Sr. Seraphim Gibbons Undergraduate Symposium Symposium

A Three-Step Synthesis of Azo Meghan E. Reilly St. Catherine University

Alexa Harnagel St. Catherine University

Ashly Solis St. Catherine University

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Reilly, Meghan E.; Harnagel, Alexa; and Solis, Ashly, "A Three-Step Synthesis of Azo Dye" (2015). Sr. Seraphim Gibbons Undergraduate Symposium. 2. https://sophia.stkate.edu/undergraduate_research_symposium/2015/Posters/2

This Event is brought to you for free and open access by the Conferences and Events at SOPHIA. It has been accepted for inclusion in Sr. Seraphim Gibbons Undergraduate Symposium by an authorized administrator of SOPHIA. For more information, please contact [email protected]. Three Step Synthesis of Azo Dye

Alexa Harnagel, Meghan Reilly, Ashly Solis St. Catherine University St. Paul, MN

Abstract Synthetic Scheme Discussion

OH Organol brown azo dye was synthesized and altered with OH O O The first two steps in the three step synthesis of Azo dye were completed conversions to see the effect it would have on its color. This allowed for the N NH2 N successfully. The first goal in this project was to synthesize compound A, testing of what reactions can be used to create new variations of azo . Azo Nanosilica N O Cl N which was completed. This can be determined using a combination of IR, dyes are organic compounds that have a R-N=N-R functional group, and are H O 2 TsOH(CAT) UV-Vis, and NMR analysis. This is shown by figures 3, 4, and 5. The IR commonly used in dyeing materials like clothing. In total three steps were NaNO 2 data shows a broad band representing an alcohol group. Two to three bands completed to synthesize and alter organol brown azo dye. In order to create O A O -1 organol brown dye 1-napthol was reacted with analine, sodium nitrate, and are visible between 1450-1600 cm , which indicates the presence of a Br silica gel. The second step converted the alcohol functional group of organol O O benzene ring. The UV-Vis data shows absorption from approximately 400- brown into a ketoester functional group. The final step of this process 600 nm which would indicate that violet, blue, green, and yellow light was N-bromosuccinimide absorbed, while orange and red light was reflected. This means that the converted an alpha hydrogen on the keto-ester to a bromine using a N photoreaction. After each step changes in UV max were recorded to see how N N compound is an orange-red dye. The NMR data for compound A is shown in CHCl N alterations in the dye affected color. The final step was attempted using hexane 3 figure 5. Approximately 5 peaks were observed from 7-9 ppm, which Benzoyl Peroxide instead of chloroform in order to make this process greener. This change was (CAT) indicated multiple aromatic rings. The synthesis of compound B was also B C more cost efficient, equally effective, and less hazardous to humans and the successful. This is shown by the NMR data in figure 6. Six peaks shown environment. The information collected in this study will be useful for finding IR, UV, and NMR Data between 7-9 ppm indicated multiple aromatic rings. A singlet at new ways to create azo dyes using more green processes. approximately 5.5 ppm indicated that a Csp2H was present in the molecule. Another singlet was observed between 1 and 3 ppm, which indicated a

96 methyl group was added. While the product was formed, unknown 95

Introduction of Azo Dye 90 impurities were found because peaks at approximately 1-3 ppm indicated the

85 presence of an unknown byproduct. Compound C was not formed. This can 1516.33cm-1 80 1456.88cm-1 be confirmed by NMR data because the data for compound C was identical 1579.92cm-1 Azo dyes were one of the earliest forms of chemistry used and are still 75 1633.69cm-1 959.54cm-1 to that of compound B, which indicated no reaction occurred. If this 1597.98cm-1 860.05cm-1 commonly found in products such as textiles and paints. Throughout 70 1385.53cm-1 875.95cm-1 Lack of absorption 1360.50cm-1 experiment was done differently, more analysis using IR would have been 3305.87cm-1 %T from 600-800 nm history, the use of dye in clothes to make colors richer was a symbol of 65 1043.32cm-1 1015.11cm-1 done. Additionally, step three would have been repeated in order to 1082.89cm-1 wealth. The diazonium intermediate allows for the addition of many 60 1147.89cm-1 826.90cm-1 successfully synthesize compound C. Furthermore, the green step would O-H 709.79cm-1 functional groups, which change the properties of the dye and in turn 55 574.12cm-1 788.41cm-1 have been included in this experiment. Using hexane as a solvent instead of 50 482.99cm-1 change the color of the dye. While it is possible to create many functional 763.97cm-1 477.78cm-1 566.33cm-1 chloroform would have resulted in a greener product. groups from the , we chose to create the organol 45 1231.54cm-1 40 39 brown dye, which dyes several materials orange. A diazonium compoud 4000 3500 3000 2500 2000 1500 1000 500450 cm-1 was synthesized from an , water and silica gel. 1-Naphthol was used Name Description Chemistry 1143 Sample 1143 By Chemistry Date Thursday, March 19 2015 with the diazonium compound to synthesize Organol Brown dye. A beta Conclusion ketoester was added onto the compound using ethyl acetoacetate in order Figure 3. IR analysis of product A Figure 4. UV-Vis analysis of product A to make a ring structure consisting of a double bond and an ester.

Chloroform, N-bromosuccinimide (NBS) and a catalytic amount of O benzoyl peroxide was added to add a bromine onto the ring structure Overall, the two of the three steps were completed successfully. The third O 2 step was not successful and the green step was not completed. This was without compromising the double bond. In order to make this three step OH 3 determined using the NMR analysis. synthesis green, it was intended to use hexane in place of chloroform. N N Hexane is more cost effective and less hazardous to the environment than N N chloroform. 1 1 Future Directions O O N OH N Br O O • Use products B and C to dye more fabric. • Use hexane in step 3 instead of chloroform. • Do an IR analysis on products B and C. 1 1 2 3 Figure 1. Functional groups used in three step synthesis of Azo dye • Try this three step synthesis using another azo dye.

Background on Green Chemistry Step References

Figure 5. NMR analysis of product A Figure 6. NMR analysis of product B • Jirandehi, H. et al, Nanosilica/NaNO2: Novel Heterogenerous System for Synthesis of Azo Compounds; Islamic Azad Univsrsity, 2010. O O Green Chemistry Comparison Table • Kuarm, S. et al, Polyvinylsulfonic acid: An Efficient and Recyclable Bronsted Acid O Br Catalyst for Pechmann Condensation; Warangal, India, 2012. O • Pavia et al. Introduction to Organic Laboratory Techniques: A Small Scale Approach; Mason, OH, 2008. N-bromosuccinimide Comparison Parameters Chloroform Hexane • Voegtle, F. et al, Bromination with N-bromosuccinimide; Wuerzburg, Germany, N N N Hazards Hazardous in case of skin contact, Hazardous in case of skin contact, 1973 Hexane N eye, ingestion, inhalation irritant. eye, ingestion, and inhalation irritant. Mutagenic for mammalian somatic Mutagenic for bacteria and yeast. Benzoyl Peroxide (CAT) B C cells, bacteria, and yeast. Chronic exposure to the substance Toxic to kidneys, liver, and heart. can produce target organs damage Acknowledgements Chronic exposure to the substance and is toxic to peripheral nervous Figure 2. Proposed green step using hexane can produce target organs damage. system. Carcinogen. Hexane is an alkane consisting of a six-carbon chain, mainly used because it This research project was funded by Minnesota Pollution Cost for solvent $8.50 $3.26 is cheap, relatively safe, unreactive, and is an easily evaporated non-polar Control Agency green chemistry curriculum initiative. Percent Yield 73% Not Determined solvent. N-hexane is commonly used as a special-purpose solvent and ° ° cleaning agent (degreaser) in the textile industry. N-hexane is also Reaction Time, Temp 10 hours, 70 C 10 hours, 70 C The authors of this project would like to acknowledge Dr. commonly used in the printing industry as a cleaner and as a component of Product Purity, byproducts Minimal Impurities Minimal Impurities James Wollack and Katelyn Caron for assisting in completion some inks and rotogravure printers. Waste produced Chloroform Hexane of this synthesis.