Synthesis of Methyl Benzoate by Fischer Esterification Sarah Preston Introduction:

An ester is an organic functional group that has an oxygen atom connected to two carbons with one of those carbons is doubly bonded to another oxygen atom. These groups are the major components of scent that is found in nature, such as flowers and fruits1. Esters are named according to the alcohol and acid they form when treated with water or hydrolyzed2. For example, methyl benzoate which is readily found in some flowers will form methanol and benzoic acid when hydrolyzed. Many of the flavorings approved by the FDA are esters, such as methyl salicylate for wintergreen, isoamyl phenylacetate for chocolate, or methyl cinnamate and ethylmethylphenylglycinate for strawberry2. There are many ways to make esters, but one of the cheapest is Fischer esterification. This process uses an acid catalyst, along with a carboxylic acid and a simple alcohol. In the case of methyl benzoate, benzoic acid is the carboxylic acid, methanol is the alcohol, and concentrated sulfuric acid acts as the catalyst. Every step in the mechanism for Fischer esterfication is reversible and depends on the equilibrium point which can be shifted by using more of one of the reactants; it is because of this reversibility of the mechanism that the mechanism for Fisher esterification is the exact opposite of hydrolysis of an ester with water1. Other ways to upset equilibrium is to remove water, in this lab anhydrous calcium chloride was used during refluxing, and so by Le Chateliers principle, the reaction will produce a higher yield of ester to compensate for the continual removal of water from the system1. Since the reaction cannot go fully to completion, the final reaction mixture for this experiment contained water, methyl benzoate, methanol, benzoic acid, and sulfuric acid. To

separate the product from unwanted products and left over reactants a few steps were taken. First, the reaction mixture was washed with water and diethyl ether so that the polar sulfuric acid and methanol would go into the water layer and the remaining less polar methyl benzoate and benzoic acid would go into the ether layer. To separate the methyl benzoate from the benzoic acid, sodium bicarbonate was added to react with benzoic acid to give off water, carbon dioxide, and a salt, sodium benzoate. The salt dissociated to form ions that went into the aqueous sodium bicarbonate layer along with the water, where as the carbon dioxide was a gas and released into the air. The ether layer can be separated and dried over an anhydrous salt to remove any residual water and since ether is a volatile solvent it evaporates easily leaving behind methyl benzoate oil. Reaction Mechanism of Fischer esterification:

Procedure:
Syntheses of methyl benzoate. In a 100mL round bottom flask 5.0g of benzoic acid and 25mL of methanol were added along with a magnetic stir bar. The flask was then cooled in ice for approximately ten minutes and 1.5mL of concentrated sulfuric acid was added along with a few boiling chips. The solution was then refluxed for one hour in a heating mantle and a stirrer directly underneath. After one hour the solution was cooled.

Isolation and purification of methyl benzoate. After cooling, the solution was decanted into a separatory funnel containing 25mL of water. The flask was rinsed with 25mL of diethyl ether and added to the separatory funnel and shaken. The water layer was drained off and the remaining ether layer was washed with 25mL of water and then 25mL of 10% sodium bicarbonate to remove unreacted benzoic acid and shaken until no reaction is apparent. The bicarbonate layer was then drained off and the remaining layer was washed with saturated sodium chloride and drained off. The remaining ether layer was dried over anhydrous calcium chloride in a 125mL Erlenmeyer flask for ten minutes. The solution was decanted into a dry 50mL Erlenmeyer flask along with 5mL of ether used to wash the drying agent. A short path mircroscale distillation was run, using a kit obtained from the stock room. The water inlet and outlet tubes were not connected because of the high boiling point of the ester could crack the glass. All product of 190oC was collected and the weighed, the percent yield was determined to be 61.38%. A TLC plate of the reaction mixture, the starting material benzoic acid, and a co-spot of the two, in a solvent system of 20% ethyl acetate in hexanes was run. A 1H NMR and a GC spectrum were obtained. Figure 1. TLC plate of reaction mixture and starting material

S=Starting material, C=Co-spot, M=reaction mixture

Figure 2. Retention values of spots on TLC plate Sample Starting material Co-spot Distance Traveled (cm) Retention Value (Rf)

Reaction mixture

Figure 3. 1H NMR of methyl benzoate oil Peak Signal (ppm) 8.039 7.480 3.899 Proton Aromatic Aromatic 1o alkyl Integration 2 2.91 3.08

Figure 4. GC analysis of methyl benzoate oil Retention Time (min) 3.215 9.967 Percent of Total Area 0.38 99.62

Discussion:
The TLC plate taken to analyze the purity of the isolated methyl benzoate mixture showed two things. The first, being that there was no starting material in the final product, this can be seen because the Rf value of the spot corresponding to the starting material is not the same as any spots in lane for the reaction mixture. Secondly, in the lanes for the co-spot and the reaction mixture were small spots that did not correlate to anything and can explained to be contaminates in the samples being tested, including the reaction mixture. However, contamination was not significant considering both the GC and 1H NMR data collected. The peak at 3.899 corresponds to the hydrogen atoms on the carbon in an ester bond. It has an integration value of 3.08 which corresponds to the three hydrogen atoms on that carbon (Figure 3). The remaining five hydrogen atoms on the benzene ring are accounted for in the remaining two peaks at 7.48 and 8.039ppm and have integration values of 2.91 and 2.00, respectively. The GC data shows two peaks at 3.215 and 9.967 minutes with area percentages of 0.38% and 99.62%, respectively (Figure 4). There was also a very large peak with a retention time of 2.329min which corresponds to the solvent used, dichloromethane. MORE. The percent yield was high at 61.68% since it would be very difficult to get the reaction to go to 100% completion. The reaction was successful, from 1H NMR it was shown that the right product was obtained with no impurities. It showed all hydrogen atoms, five on the benzene ring and three on the methyl group. The GC showed SOMETHING. Also, the TLC plate gave qualitative analysis that there were few impurities in the reaction mixture and that there was not any starting material left. Finally, no problems arose when conducting the experiment and the percent yield was

61.38%.

References:
1

Williamson, K. L. http://courses.chem.psu.edu/chem213. Experiment 84: A Floral Fragrance, Methyl Benzoate.

Clark, Jim. http://www.chemguide.co.uk/organicprops/esters/background.html. Introducing Esters.