Preparation of DEET Devin Roy April 1, 2012 The preparation of N,N-dimethyl-m-toluamide also known as DEET was carried out

through the Schotten-baumann synthesis method. N,N-Diethyl-meta-toluamide, abbreviated DEET, is a slightly yellow oil. It is the most common active ingredient in insect repellents. It is intended to be applied to the skin or to clothing, and provides protection against tick bites, mosquito bites, chiggers, and other insects that can transmit disease. DEET was developed by the United States Army, following its experience of jungle warfare during World War II. It was originally tested as a pesticide on farm fields, and entered military use in 1946 and civilian use in 1957. It was used in Vietnam and Southeast Asia.

Introduction The SchottenBaumann reaction is a method to synthesize amides from amines and acid chlorides. Sometimes the name for this reaction is also used to indicate the reaction between an acid chloride and a alcohol to form an ester. The reaction was first described in 1883 by German chemists Carl Schotten and Eugen Baumann. In the first step an acid chloride reacts with an amine so that an amide is formed, together with a proton and a chloride ion. Addition of a base is required to absorb this acidic proton, or the reaction will not proceed. Often, an aqueous solution of a base is slowly added to the reaction mixture. The name "Schotten-Baumann reaction conditions" is often used to indicate the use of a two-phase solvent system, consisting of water and an organic solvent. The base within the water phase neutralizes the acid, generated in the reaction, while the starting materials and product remain in the organic phase, often dichloromethane or diethyl ether. Results and Discussion

Chemical m-toluic acid A B c

Signal 2.5 7.6 11.1

Peaks S M S

# of H's 3 4 1

Structure CH3-Ph 4H's on Ph ring C-OH

Diethyl hydrochloride

1.5

CH3-CH2 \ N / CH3-CH2 CH3-CH2 \ N / CH3-CH2

3.1

DEET

1.0

2.1

CH3-CH2 \ N / CH3-CH2 CH3-Ph

DEET Continued

3.4

D Chemical m-toluic acid

7.2

M cm^-1

CH3-CH2 \ N / CH3-CH2 4H's on Ph ring Interpretation

2867 745 2500-3200 1681

C-H Sp3 stretch C-H bend(3 adjacent H's) Carboxylic Acid stretch C=O stretch

Diethyl hydrochloride

2970 350

C-H Sp3 stretch N-H stretch

DEET

2970 1632 796

C-H Sp3 stretch C=O stretch C-H bend (3 adjacent H's)

No % yield was able to be obtained because at the end of this experiment we still had liquid form DEET and no solid, so solvent was still present and the concentration was not known precisely. This was done at the request of Mrs. Williams. Conclusion DEET was indeed formed judging from the above NMR and IR spectra intepretations, as well as the smell present at the end of the experiment. DEET has a very distinctive smell if you've ever used it outdoors to repel misquitos. Experimental Section Addition under reflux was performed on m-toluic acid with thionyl chloride for 20 minutes. HCL gas evolved and when this ended it signaled the end of this first step. The mix was then cooled in an ice bath to 10 degrees celsius or below. NaOH was then cooled in an ice bath separately for 5 minutes. diethylamine hydrochloride and sodium lauryl sulfate was added to said NaOH in small portions while swirling. This was mixed into the solution from the first section while still on ice and also stirring over the course of 5 minutes. This was then heated using a hot water bath for approximately 15 minutes. At this point the solution should be basic. The acid chloride odor should also be gone. The mix was then allowed to cool to room temperature and transferred to a separatory funnel and extracted with 3 portions of ethyl ether and then washled with NaCL and HCL 1M. the solution was then dried using

MgSO4 to remove any excess H2O remaining. The excess ethyl ether was then boiled away using the roto-evap apparatus. References www.wikipedia.com