Memorandom To: Bonds and Lampard Partnership Ms. Jennifer Hurst, Legal Assistant to Ms.

Coker, LLS Suite 1401 1030 West Main Street Topeka, Ks 34721

From: Georgianna Techus Research Student: Nam Tu Georgia Tech Date: March 30, 2012 The synthesis of methyl 3-nitrobenzoate was attempted from the reaction between methyl
benzoate (0.30 mL, 136.15 g/mol, 1.094 g/mL density) and nitric acid (0.2 mL, 63.01 g/mol). The carboxyl group in methyl benzoate needed to be protonated by adding sulfuric acid (0.6 mL, 98.07 g/mol). During the reaction time, the mixture was kept in an ice bath and constantly stirred. After letting the reaction to finish, the mixture was poured to 2.5g (+ - 0.5 g) of ice. A filter was used to collect a pale yellow solid, the initial product. Small amount of product was used to test the ability of 3 solvents. The right solvent for methyl 3-nitrobenzoate was methanol. With methanol, recrystallization was

performed on initial product to obtain pure methyl 3-nitrobenzoate, which had a white color.
The percent yield of the first product and second product were .. and 2.7% respectively. The data and calculations for these yields can be found in the attached documents. Data and calculation are

represented below.

The examination of the H1NMR and IR spectra proves that the reaction did proceed as desired. First, the methyl benzoate H1NMR spectra showed eight hydrogens, and the methyl 3-nitrobenzoate spectra showed only seven. Second, the reactants spectra showed only 3 groups of aromatic hydrogens (7.4 ppm, 7.5 ppm, 8.0 ppm) while the products spectra showed 4 different aromatic hydrogens (7.6 ppm, 2 @ 8.4 ppm, 8.9 ppm). Both of these results aid in proving that a hydrogen was replaced by another group on the aromatic ring. The main difference in the IR spectra was the presence of a peak at 1526.1 cm-1 in the methyl 3-nitrobenzoate spectrum. The location of this peak is directly caused by the N-O bond in the product, which means that an NO2 group successfully replaced the aromatic hydrogen. Additional data and analysis can be found in the attached documents.

Nam Tu

Georgia Tech Resonance (ppm) Methyl Benzoate A B C D methyl 3nitrobenzoate A B C D Integration multiplicity Coupling constant (Hz) Identification

3.9 7.4 7.5 8

3 2 1 2

singlet Aromatic Multiplet Aromatic Multiplet Aromatic Multiplet

H in methyl group 14.7 7.2 8.4 Aromatic Hydrogen Aromatic Hydrogen - position 4th in the ring Aromatic Hydrogen

4 7.6 8.4 8.8

3 1 2 1

singlet Aromatic Multiplet Aromatic Multiplet Aromatic Multiplet

15.9 24.9 3.9

H in methyl group Aromatic Hydrogen - position 4th in the ring Aromatic Hydrogen Aromatic Hydrogen

Bending Position (cm-1) Methyl Benzoate 1731.3

Stretching Position (cm-1)

2949.5 and 3005.5 3073.9 1115.9 and 1283.7 methyl 3nitrobenzoate 1526.1 1352.1 1134.6 1718.8 2965.8 and 3011.7 3098.7

Assignment Phenyl Ring Substitution Overtones C-H C-H CH3 deformation

asymmetrical stretch symmetrical stretch CH3 deformation Phenyl Ring Substitution Overtones C-H C-H