18 July 2012 Professor Herrera. CHEM 245 Lab.

Week 10 Lab Report Electrophilic Aromatic Substitution ABSTRACT

Max Morris

Electrophilic aromatic substitution is governed by the directing nature of the substituent groups attached to benzene. The results of a bromination of acetanilide and 4-methylacetanilide were studied to investigate the substitution directing nature of acetamide and methyl substituent groups on benzene. The bromination of acetanilide and 4-methylacetanilide yielded 4bromoacetanilide and 2-bromo-4-methylacetanilide respectively, as predicted by the ortho/para directing and moderately activating nature of acetamide. RESULTS The bromination of acetanilide and 4-methylacetanilide yielded 4-bromoacetanilide and 2bromo-4-methylacetanilide respectively. Both synthesized products were a white solid. The yield and results of melting point analysis are provided in Table 1. The spectra from 1H NMR (proton nuclear magnetic resonance) analysis of 4-bromoacetanilide is provided in Figure 1. The spectra from 1H NMR analysis of 2-bromo-4-methylacetanilide is provided in Figure 2. Table 1. Yield and melting point analysis of bromination products. Yield (% yield) 4-bromoacetanilide 2-bromo-4methylacetanilide 0.279g (68.0%) 117.8 - 119.0 118.1 - 119.7 Experimental Melting Point Ranges (C) Reported Melting Point Range (C) 168 118 - 120

DISCUSSION

18 July 2012

Max Morris

The yields of [XXX]% and 68.0% are reasonable considering handling losses from material transfers, filtration, and recrystallization. The experimental melting point rangers are close to the reported values. Bromination of acetanilide yielded 4-bromoacetanilide due to the ortho/para-directing nature of acetanilide. Substitution to the ortho-position experienced hinderance due to the large, bulky character of the acetamide group. Therefore, the major product of the substitution was to the para-position, 4-bromoacetanilide. Bromination of 4-methylacetanilide yielded 2-bromo-4-acetanilide primarily due to the ortho/para directing nature of the acetamide group and the para location of the methyl group. The starting product, 4-methylacetanilide, has two ortho/para-directing groups: a methyl and an acetamide. Additionally, the placement of the substituent groups as para to each other restricts substation to the ortho positions. The moderately activating acetamide group is much more directing than the weakly deactivating methyl group, therefore substitution is most likely to occur ortho to acetamide at the 2-position. A mechanistic analysis of acetanilide electrophilic substitution reveals that acetanilide substitutes mainly at the para position because of resonance stabilization as nitrogen accepts an electron pair from the benzene ring and adopts a positive charge. The rate is slower than analine because the substituent acetyl group on the amine in acetamide is electron donation, making acetamide slightly less able to accept the electron pair from benzene in comparison to analine itself. REFERENCES Darer, A. (2012) CHEM 245 Lab Notebook pp [XXX] Experiment 20 adapted by Nellis (2012) Mohrig et al. Modern projects and experiments in organic chemistry (2E) pp163-170. Mohrig et al. (2010) Techniques in organic chemistry (3E) Techniques 7.4, 15.3, 15.6, 21.