Lab 10b: DEET, an Insect Repellent

Student: David Maestas

Teaching Assistant: Dr. J
Class: CHEM 243b Section 12
Date of Experiment: 4-7-2014














DISCUSSION:
This lab included the synthesis of DEET, a common insect repellent. Its synthetic scheme has
logical sense by following the reactivity level of carbonyls. In this case, the starting material of
m-toulic acid is a simple carboxylic acid. Since a typical amine is basic and would immediately
cause an acid-base reaction with a carboxylic acid, excess thionyl chloride is used. This is very
useful in the synthesis because the thionyl chloride acts to with the m-toulic acid to remove the
OH group and replace it with a chloride. Since acyl chlorides are very reactive due to the
polarities between the carbonyl center and the chloride, the chloride can be readily removed in
many ways. The temperature of the reaction is kept near 90 C to ensure full completion. After
the OH is removed, the m-toulic chloride is reacted with excess diethylamine dropwise at room
temperature. This synthesis step is used to add the diethylamine to the carbonyl center and
replace the chloride. The reason it is added dropwise is both to provide safety (the reaction can
release noxious gasses) and to ensure that the product is the desired DEET. Since many of these
reactions depend on pKa values, and relative carbonyl reactivity, it is important to note that acyl
chlorides are far more reactive than carboxylic acids. After the acid is replaced by the chloride, it
because much easier for an amide to take its place due to their relative reactivity.

The extraction procedure, or workup, was used to help obtain mostly the desired product of
DEET while leaving behind other side products. NaOH, in aqueous solution, was added in the
workup because it should react with any remaining acid chloride and form a sodium salt of
original carboxylic acid. This carboxylic acid is soluble in the aqueous layer during the
extraction process. In addition, diethylamine hydrochloride (a side product) is also water soluble
so will solvate it into the aqueous layer. The water is coming from being the solvent for the
NaOH and also it is used to wash the ether layer. Finally, any remaining thionyl chloride will be
destroyed by the water added, and will result in forming SO
2
gas and HCl which is ultimately
neutralized by the NaOH. Since water is now in the organic layer, it is removed by sodium
sulfate. The addition of sodium sulfate acts to bind strongly to water and dry the organic product
by pulling the water down to the bottom of the test tube or vial. At the end of the extraction, a
filtering process is used. For this case an alumina column was selected with a hexanes eluent.
The alumina column is used is a separation technique based on solid-liquid phase partitioning.
Since the alumina is very polar, any polar substances in the organic layer will be removed,
leaving a purified product. Any remaining hexanes used for eluent is then evaporated off with a
hot plate. This process should remove any polar substances like water.

For this experiment, the identification of the final product and comparison to what it should be
was performed. The results showed that the final DEET liquid did match the expected tan
colored liquid. The second process was to perform an IR spectroscopy and compare it to the
expected values from the structure of the DEET molecule (shown in the lab manual) and to the
IR spectra example shown in the lab manual. Since the DEET molecule has a phenol group
attached, the IR spectra should show a C-H bond in the ~3030cm
-1
region. Also, since the final
product is a carbonyl attached to an amide group, a C=O stretch should appear in the 1690
1630 cm
-1
area. The lab manual shows several more peaks that are not shown in typical IR
tables. From the actual IR spectra performed, all of the expected peaks matched. This shows that
there experiment was generally successful. Once problem did arise at the very end. Since the lab
manuals instructions were very vague, the hexanes used from the alumina column were
evaporated off, but it was very unsure how much evaporation is too much. The final product
had a yield of 244%. While this percentage is very high, it is expected that all of the hexanes
were not evaporated away. If this step could be performed again, a mass would be taken of how
much hexanes were actually used, and then a rough estimate could be made of how much to
evaporate off without possibly damaging the product. Since the IR spectra of the two compared
match very well, it is assumed that the experiment was a success, only not all the hexanes were
removed, causing the yield to look terrible.