METHYL BENZOATE

Ph-C02H + MeOH Ph.C02Me + H20

In a 500-ml round-bottomed flask place a mixture of 30g (0.246mol) of benzoic acid, 80g
(101 ml, 2.5 mol) of absolute methanol and 5 g (2.7ml) of concentrated sulphuric acid. Add a
few small chips of porous porcelain, attach a reflux condenser and boil the mixture gently for
4 hours (1). Distil off the excess of alcohol on a water bath (rotary evaporator) and allow to
cool. Pour the residue into about 250 m1 of water contained in a separatory funnel and rinse
the flask with a few m1 of water which are also poured into the separatory funnel. If, owing
to the comparatively slight difference between the density of the ester and of water, difficulty
is experienced in obtaining a sharp separation of the lower ester layer and water, add 1&15
m1 of carbon tetrachloride (2) and shake the mixture in the funnel vigorously; upon standing,
the heavy solution of methyl benzoate in the carbon tetrachloride separates sharply and
rapidly at the bottom of the separatory funnel. Run off the lower layer carefully, reject the
upper aqueous layer, return the methyl benzoate to the funnel and shake it with a strong
solution of sodium hydrogen carbonate until all free acid is removed and no further evolution
of carbon dioxide occurs. Wash once with water, and dry by pouring into a small dry conical
flask containing about 5 g of magnesium sulphate. Stopper the flask, shake for about 5
minutes and allow to stand for at least half an hour with occasional shaking. Filter the methyl
benzoate solution through a small fluted filter paper directly into a round-bottomed flask
fitted with a still-head carrying a 360C thermometer and an air condenser. Add a few boiling
chips and distil from an air bath; raise the temperature slowly at first until all carbon
tetrachloride has passed over and then heat more strongly. Collect the methyl benzoate (a
colourless liquid) at 198-200 "C. The yield is 31 g (92%).

Notes:
(1) Slightly improved results may be obtained by increasing the time of heating.
(2) Alternatively, the ester may be extracted with two 50ml portions of ether. The ethereal
solution is washed with concentrated sodium hydrogen carbonate solution (handle the
separatory funnel cautiously as carbon dioxide is evolved) until effervescence ceases, then
with water, and dried over magnesium sulphate. The ether is removed by flash distillation and
the residual ester distilled.
Cognate preparations
[The p.m.r. spectra (CDC13 or CC14, TMS) of the ethyl, propyl and butyl esters should be
recorded and interpreted, since the signals corresponding to the protons of these alkyl groups,
afford good examples of the (N + 1)(M + 1) rule for multiplicity (p. 341).] I Ethyl benzoate
(sulphuric acid as a catalyst). Use 30 g (0.246 mol) of benzoic 6.14 PRACTICAL ORGANIC
CHEMISTRY acid, 115 g (145 ml, 2.5 mol) of absolute ethanol and 5 g (2.7 ml) of
concentrated sulphuric acid. Reflux the mixture for 4 hours and work up as for methyl
benzoate. The yield of ethyl benzoate, b.p. 212-214,"C, is 32g (86%).
Propyl benzoate. Into a 500-ml round-bottomed flask place 30g (0.246 mol) of benzoic acid,
30g (37.5 ml, 0.5 mol) of propan-1-01, 50ml of sodium-dried toluene and log (5.4ml) of
concentrated sulphuric acid. Reflux the mixture for 10 hours. Pour the reaction product into
about 250ml of water, and extract with ether. Wash the ethereal extract with saturated sodium
hydrogen carbonate solution and then with water: dry over magnesium sulphate. Distil off the
ether and some of the toluene through a fractionating column, and distil the residue from a
Claisen flask. Collect the propyl benzoate at 229- 230 "C. The yield is 37 g (9 1%).
Butyl benzoate. Use 30 g (0.246 mol) of benzoic acid, 37 g (46 ml, 0.5 mol) of butan-1-01,
50 m1 of sodium-dried toluene and 10 g (5.4 ml) of concentrated sulphuric acid, and reflux
the mixture for 12 hours. Work up the product as for propyl benzoate; after the ether and
toluene have been removed with the aid of a rotary evaporator, distil the residue under
reduced pressure. The yield of butyl benzoate, b.p. 119-120 "Cl1 l mmHg, is 35 g (80%).
Methyl salicylate. Use 28 g (0.2 mol) of salicylic acid, 64 g (8 1 ml, 2 mol) of dry methanol
and 8 m1 of concentrated sulphuric acid. Reflux the mixture for at least 5 hours and work up
as for methyl benzoate. Collect the pure methyl salicylate (a colourless oil of delightful
fragrance, 'oil of wintergreen') at 221- 224 "C; the yield is 25 g (81%). The ester may also be
distilled under reduced pressure; the b.p. is 115 "C/20 mmHg and a 2 "C fraction should be
collected.
Ethyl salicylate. This colourless ester, b.p. 231-234 "C, is similarly obtained in 75 per cent
yield from salicylic acid, ethanol and sulphuric acid as catalyst. It is best to distil the ester
under reduced pressure; the boiling points under various pressures are given in Table 2.10.
Methyl cinnamate. Use 59 g (0.4 mol) of cinnamic acid (Expt 6.1 38), 128 g (162 ml, 4mol)
of absolute methanol and 6 m1 of concentrated sulphuric acid; reflux the mixture for 5 hours.
Remove excess methanol, pour the residue into about 500ml of water and add 300ml of ether.
Separate, wash and dry the ether solution in the usual way. Remove the ether on a rotary
evaporator; the residue crystallises on cooling, yielding 58 g (90%) of methyl cinnamate,
m.p. 33-34C. To obtain a pure specimen, m.p. 36 "C, dissolve a sample in the minimum of
methanol maintained at 30 "C in a water bath, and add water slowly from a dropping pipette
with stirring until the oily ester just begins to separate. Seed the solution and transfer rapidly
to an ice bath with a glass rod, scratching the sides of the vessel vigorously with a glass rod.
Filter the resulting colourless needles rapidly.
Ethyl nicotinate (ethyl pyridine-3-carboxylate). Reflux a mixture of 37 g (0.3 mol) pure
nicotinic acid (Expt 6.150), 92 g (1 15 ml, 2 mol) of absolute ethanol and 90g (50 ml) of
concentrated sulphuric acid on a steam bath. Cool the solution and pour it slowly and with
stirring on to 200g of crushed ice. Add sufficient ammonia solution to render the resulting
solution strongly alkaline: generally, some ester separates as an oil but most of it remains
dissolved in the alkaline solution. Extract the mixture with five 25 m1 portions AROMATIC
COMPOUNDS 6.14 of ether, dry the combined ethereal extracts over magnesium sulphate,
remove the ether by flash distillation and distil the residue under reduced pressure. The ethyl
nicotinate distils at 117-1 18 "C116 mmHg; the yield is 32g (71%). The boiling point under
atmospheric pressure is 222-224 "C.