1.

PREPARATION OF METHYL BENZOATE

SAFETY DATA
Dichloromethane
HARMFUL

Wear protective gloves.

RESIDUES TO CHLORINATED WASTE SOLVENTS.

Methanol Sulphuric acid (conc)

FLAMMABLE, TOXIC CORROSIVE, CAUSES BURNS

Do not heat over flame. Prevent contact with skin; wash spills with large quantities of water

INTRODUCTION Many esters can be prepared by the reaction of an alcohol with a carboxylic acid, particularly if the alcohol is primary or secondary:O R C OH + R' OH O H
+

OR'

+ H2O

The process is reversible but equilibrium is reached only slowly unless the reaction is catalysed by a small amount of mineral acid such as sulphuric acid (the H+ above the equilibrium arrows). By using an excess of the alcohol, if this is reaily available, the reaction can be driven to completion with respect to the carboxylic acid. [Hart. Organic Chemistry 8th edn. pp. 282-285 gives details of the mechanism of this reaction.] In this experiment, methyl benzoate will be prepared by the sulphuric acid-catalysed esterification of benzoic acid with methanol. A large excess of methanol is used, thus the yield calculation can be based on the amount of benzoic acid taken.
O C OH + CH3OH O C OCH3 + H2O

benzoic acid

methanol

methyl benzoate

EXPERIMENTAL PROCEDURE Place benzoic acid (12.2 g and methanol (35 ml) in a 250 ml round-bottomed flask. Swirl to dissolve the benzoic acid, then add concentrated sulphuric acid (1.5 ml) slowly down the wall of the flask. Again, swirl to mix the contents of the flask, add two or three anti-bumping granules (small glass beads), fit a reflux water condenser and heat the solution on a steam bath for an hour (or longer if convenient). By this point in the procedure the methyl benzoate has been prepared but is still mixed with sulphuric acid, water and excess methanol. The next step is to extract the product from the mixture.

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Consult a demonstrator on the use of the rotary evaporator and distil off the excess methanol. Pour the residue into a small separating funnel using dichloromethane (about 50 ml) to rinse the flask into the funnel. Add about 20 ml of water to the funnel, shake and separate, keeping the LOWER organic layer which now contains the dissolved ester. The remaining aqueous layer can be discarded. Return the organic layer to the funnel and shake with 10% sodium hydrogen carbonate solution (20 ml) to neutralised the sulphuric acid. Again, separate the lower organic layer and discard the aqueous layer. Repeat the 10% sodium hydrogen carbonate washing once more and then run the methyl benzoate solution into a small conical flask. Dry the solution by adding an anhydrous sodium sulphate (about 2 g) in portions with swirling, leave for 10 minutes, then filter the solution into a 50 ml round bottom flask using a few ml of dichloromethane to rinse the drying agent. After consulting a demonstrator, carefully distil off the dichloromethane on a rotary evaporator. A demonstrator will now show you how to set up the distillation apparatus. Using a small flame, distil the methyl benzoate at atmospheric pressure (take care not to heat the reaction too fiercely, otherwise you will char the reaction). Discard any material boiling below 190oC then, using a clean, pre-weighed receiving flask, collect the fraction that distils above 190oC. Use a Pasteur pipette to transfer your sample to a clean, pre-weighted sample vial. Record the boiling range and weigh the product. Calculate the percentage yield and submit a specimen of product. After consulting a demonstrator, record the infrared spectrum of your product as a liquid film. Read the notes on infrared spectroscopy and identify the C-H and C=O absorptions in the spectrum.

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SAFETY INFORMATION SHEET

1. PREPARATION OF METHYL BENZOATE
This information must be read before the experiment is attempted. You are required to sign the declaration at the bottom of the page and have this countersigned by a demonstrator before commencing the practical. Do not sign this form until you are satisfied that you appreciate the risks associated with all aspects of the experiment.
Dichloromethane
HARMFUL

Wear protective gloves.

RESIDUES TO CHLORINATED WASTE SOLVENTS.

Methanol Sulphuric acid (conc)

FLAMMABLE, TOXIC CORROSIVE, CAUSES BURNS

Do not heat over flame. Prevent contact with skin; wash spills with large quantities of water

I have read the risk assessment and will comply with these procedures. Name (Please print) Signature Group Date

Demonstrator's Signature

CAREFULLY TEAR THIS SHEET FROM YOUR LABORATORY MANUAL AND HAND IT TO A DEMONSTRATOR

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