Synthesis of Benzocaine

Davide Giordano: davideg@student.ethz.ch 23. November 2009

Assistant: Rui Wang

1 Theory
1.1 Reaction

1.2 Mechanism

2 Toxicological data
p-aminobenzoic acid R22 R36/37/38 R43 S26 S36 EtOH R11 S7 S16 R35 R35 S26 S30 Harmful if swallowed Irritating to eyes, respiratory system and skin May cause sensitisation by skin contact In case of contact with eyes, rinse immediately with plenty of water and seek medical advice Wear suitable protective clothing Highly flammable Keep container tightly closed Keep away from sources of ignition - No smoking Causes severe burns Causes severe burns In case of contact with eyes, rinse immediately with plenty of water and seek medical advice Never add water to this product

H2S04

S45 Benzocaine R43 R36 S24/25 S37 S24/25

In case of accident or if you feel unwell seek medical advice immediately (show the label where possible) May cause sensitisation by skin contact Irritating to eyes Avoid contact with skin and eyes Wear suitable gloves Avoid contact with skin and eyes

NaHCO3

3 Experimental Tasks
3.1 Equipment

3.2 Procedure
Reaction: 5.4350 g of p-aminobenzoic acid were placed in a 500ml round flask and then 80ml of ethanol (99% puriss.) were added. It has been swered gently to help dissolve the solid. 5ml of concentrated sulfuric acid were carefully added. A reflux condenser was attached and the mixture stirred for 75 at 130 C in oil bath. Isolation: The mixture was cooled down to room temperature in ice bath, then the contents was transferred to a 250ml beaker and neutralized cautiously with dropwise addition of sat. Na2CO3 solution until the pH was approximately above 7. (A huge was needed; it was difficult to reach basic pH). Some water was added and the mixture cooled in an ice bath for 15min to complete the crystallization process. The crude product was collected by vacuum filtration. Recrystallization: The crude product were put in a round flask and heated up till 120C. Hot ethanol was added dropwise and until all the oil was dissolved. A small amount of hot water was added droop wise solution until cloudiness was appeared and then again a few drops of ethanol were added. The mixture was stirred while cooling in an ice bath. Finally the Benzocaine was collected by vacuum filtration and kept in the fume hood overnight to dry.

reactant p-aminobenzoic acid H2S04 EtOH

molar weight [g/mol] 137.14 98.08 46.07

density (20C) [g/cm3] 1.380 1.84 0.79

volume weight quantity equivalent [ml] [g] [mol] -5 80 5.435 9.200 63.200 0.040 0.094 1.372 1 >2 >34

melting point [C] 188-189 337 -114

4 Characterization
4.1 Literal physical data
product Benzocaine molar weight melting point [g/mol] [C]
165.19

88-90

4.2 Results
mass of the received Benzocaine: measured melting point: yield: IR-Spectroscopy: 4.062g = 0.025mol 85.9 86.8C 62.0%

IR bands [cm-1] 3420 3222 2985 2957 2900 1679 1594 1514 - 1441

interpretation N-H valence arom. C-H(sp2) valence aliph. C-H(sp3) valence C=O (?) arom. C=C valence

5 Discussion
I do not have much to say: the yield is ok, purity shouldnt be bad, because by comparing the measured IR-Spec. to a literal one, you will see that all bands are here, this time also the intensity is ok (except 1170 882 and the last part of the fingerprint region). Also I have to say, that the interpretation of the bands wasnt easy, I had difficulties to find e.g. the values for C=O which in true should be above 1700.

Just the measured melting point wasnt very well, I dont know, may be there where some remaining solvent. Or maybe the last step of the recrystallization wasnt done in the right way (oli water EtOH).

6 References
[1] SIGMA-ALDRICH Date accessed: 16.11.2009 on http://www.sigmaaldrich.com [2] Nachhaltigkeit im organisch-chemischen Praktikum Date accessed: 16.11.2009 on www.oc-praktikum.de [3] Merck Chemicals (2009) Product catalog Online Database. Date accessed: 16.11.2009 on http://www.merck-chemicals.de/ [4] Spectral Database for Organic Compounds, SDBS Date accessed: 16.11.2009 on http://riodb01.ibase.aist.go.jp/sdbs/cgibin/direct_frame_top.cgi

7 Appendix
Lab journal (copy) Literal IR spectroscopy [4] IR spectroscopy Procedure [2] Physical data & safety [1],[3]