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Benzocaine (2 Steps)
Benzocaine (2 Steps)
Benzocaine (2 Steps)
04.11.2007
Organic chemistry practical course (OCP1)
HS 07/08
Lorenz Schwarzer
D-Biol
Synthesis of Benzocaine
(ethyl-4-aminobenzoate)
CH3
H2N
O
Method
1. Reduction
Reaction equation
O OH OH
Sn
N H2N
O O O
Para-nitrobenzoic acid
Molar weight 167.12 g/mol
Density 1.58 g/ml
Melting point 237 C
Boiling point Sublimes C
O OH
R-Phrases R22 Harmful if swallowed.
N R41 Risk of serious damage to the
O O eyes.
S-Phrases S26 In case of contact with eyes, rinse
immediately with plenty of water
and seek medical advice.
S39 Wear eye / face protection.
Tin
Molar weight 118.71 g/mol
Density 7.265 g/ml
Sn Melting point 231.93 C
Boiling point 2602 C
R-Phrases
2
S-Phrases
Hydrochloric acid (conc.)
Molar weight 36.46 g/mol
Density 1.19 g/ml
Melting point -40 C
Boiling point 84 C
H-Cl R-Phrases R 34 Causes burns
R 36 Irritating to eyes
R 37 Irritating to respiratory system
R 38 Irritating to skin
S-Phrases S 26 In case of contact with eyes, rinse
immediately with plenty of water
and seek medical advice.
Ammonia
Molar weight 17.03 g/mol
Density 0.69 g/ml
Melting point -77.73 C
Boiling point -33.34 C
R-Phrases R10 Flammable
H R23 Toxic by inhalation
H N R34 Causes burns
H R50 Very toxic to aquatic organism
S-Phrases S1/2 Keep locked up and out of the
reach of children
S16 Keep away from sources of
ignition no smoking
S36/37/39 Wear suitable protective
clothing, gloves and eye/face
protection
Educts
3
Experimental accomplishment
1. 2.89g p-nitrobenzoic acid, 7.04g Tin (little balls) and 15ml conc. HCl were put
in a round bottom flask (fitted with a reflux condenser). The mixture was
heated up to 115C for about 20min (caution gases). The solution becomes
clear.
2. The solution is decanted and the remaining tin washed with water and
decanted again.
3. With conc. Ammonia the solution is adjusted to pH 9, and then it was heated
up again for 20min. Filtered with vacuum.
4. The solvent was evaporated with vacuum.
5. The crystals were recristallized from ethanol/water (2:8)
Experimental setup
Reflux condenser
Thermometer
Filter
Oilbath
67 67
4 5 4 5
3 8 3 8
11 9 9
21 2
Vacuum
1 1
0
4
Results
If you compare the IR-spectrum of the product with the Reference spectrums of p-
aminobenzoic acid and p-nitrobenzoic acid, you can see that most of the product is
still p-nitrobenzoic acid. The reduction of p-nitrobenzoic acid didnt go well.
One reason could be that we used tin as balls instead of powdered tin.
For the esterification of the p-aminobenzoic (PABA) acid to benzocaine I had to take
some PABA from the Assistant
5
Reference IR-spectrum of p-aminobenzoic acid
6
2. Esterification
Reaction equation
CH3
OH O
H 2S O 4 / E tO H
H2N H2N
O O
Mechanism
CH3
CH3
+ O +
O OH HO OH H
HO OH HO O
+ OH
C HO OH
CH3
+
H
Ethanol
Molar weight 46,07 g/mol
Density 0.79 g/ml
Melting point -114.4 C
OH Boiling point 78.37 C
H3C R-Phrases R11 Highly flammable
S-Phrases S7 Keep container tightly closed
S16 Keep away from sources of
ignition
7
Sulfuric acid (H2SO4)
Molar weight 98,07 g/mol
Density 1.84 g/ml
Melting point 10 C
Boiling point 338 C
R-Phrases R35 Causes severe burns
HO S-Phrases S1/2 Keep locked up and out of the
O
S reach of children
O S26 In case of contact with eyes, rinse
OH immediately with plenty of water
and seek medical advice.
S30 Never add water to this product
S45 In case of accident or if you feel
unwell, seek medical advice
immediately
Benzocaine
Molar weight 165.19 g/mol
Density 1.17 g/ml
Melting point 89-92 C
Boiling point 172 C
CH3
R-Phrases R36/37/38 Irritating to eyes, respiratory
system and skin
O
R43 May cause sensitization by skin
H2N
contact
O
S-Phrases S24 Avoid contact with skin
S26 In case of contact with eyes, rinse
immediately with plenty of water
and seek medical advice
S37/39 Wear suitable gloves and eye /
face protection
8
Educts
Experimental accomplishment
1. 3.12g PABA from the Assistant (reduction didnt work), 15ml of ethanol and
1ml of H2SO4 were added to a bottom flask. The Solution was heated under
reflux for 2h (with stirrer).
2. Then cooled down and neutralized with 10% Na2CO3 until the pH was over 9.
3. Extracted with ether in the separation funnel. Dried with sodium sulphate.
4. The ether and ethanol were evaporated. A white powder appeared.
Experimental setup
Reflux condenser
Thermometer
Oilbath
67 67
4 5 4 5
3 8 3 8
11 9 9
21 2
1 1
0
9
Results
With the aid of the comparisons of the token IR-spectrum with the reference
spectrum, it is not clear if the product is PABA or Benzocaine, but if you compare the
token melting point with the literature values of BABA and Benzocaine, the product
can be identified as benzocaine.
10
Reference IR-spectrum of benzocaine
Literature
CrossFire Beilstein
http://riodb01.ibase.aist.go.jp/sdbs/cgi-bin/cre_index.cgi?lang=eng
http://en.wikipedia.org
http://www.chemexper.com
http://www.chemblink.com
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