Synthesis of an Alkyl Halide

Ruther Harvey Idiong Cabral Institute of Biology, University of the Philippines, Diliman, Quezon City 1101 Philippines Date Performed: July 9, 2013; Date Submitted: July 18, 2013. Although alkyl halides are less encountered in nature, the reactions that occur to them act as a model for similar, but more complex reactions. One of such reactions is the nucleophilic substitution. In this experiment, tert-butyl chloride, an alkyl halide, was synthesized from tert-butyl alcohol. The mechanism in this reaction is an SN1 reaction, which means substitution, nucleophilic, unimolecular. Only 1 mL of tertbutyl chloride was produced, with a percent yield of 8.63%. The low yield in the experiment may be caused by different factors, including experimental and instrumental problems. Improving experimental conditions and instruments were recommended to improve the accuracy of the experiment. Introduction There are thousands of halogensubstituted organic compounds that are present in nature. Such substances have various applications in different fields, such as medicine and food. An alkyl halide is an example of such compound. Although alkyl halides are less encountered than other organohalides, the reactions they undergo are very much encountered. These reactions include nucleophilic substitutions and eliminations. Thus, the reactions of alkyl halides are studied to substitute similar, but more complex, reactions that occur in other molecules1. The most useful method of preparing alkyl halides is to synthesize them from alcohols. The simplest method of preparing alkyl halides is to treat alcohol with hydrogen halides (HCl, HBr, HI). This kind of reaction is more effective with tertiary alcohols. It reacts in the following reaction1. (1) In this experiment, tert-butyl chloride was prepared from tert-butyl alcohol and hydrochloric acid. Simple distillation was used as the purification method in the experiment. Experimental Details For this experiment, a dry 30-mL separatory funnel was used for the reaction of 10 mL tertbutyl alcohol and 20 mL cold, concentrated HCl. The mixture was swirled gently. After letting the mixture stand for 20 minutes, the lower layer, which was the water, was drained using a setup similar to Figure 1. After the getting the aqueous layer, the organic layer was then obtained.

Figure 1. A setup to drain the layers in a separatory funnel The organic layer was then placed in a flask containing solid NaHCO3. This is to remove excess acid in the organic layer. A solid NaHCO3 was used to avoid adding more water to the organic layer2. The solution was then decanted to another flask, and anhydrous CaCl2 was added to remove traces of water in the solution2. Before distillation, boiling chips

were added to have more bubble formation sites, and thus ease the boiling3. It is also used to avoid superheating the solution4. For the purification process, a simple distillation was used in the experiment. This was done via a simple distillation set-up, as seen in Figure 2, which contains a heated distillation flask, where the crude solution was placed, a condenser, with continuous flow of cold water, and a receiving flask in an ice bath, amongst all other things. The continuous flow of water was needed to avoid making the water warm, which would make the distillation ineffective4. The fraction that was collected in the 49C-52C range was considered the purified product.

of configuration and second-order kinetics are observed in such a reaction. SN2 stands for substitution, nucleophilic, bimolecular. Most nucleophilic reactions take the SN2 pathway. SN2 reactions favour a ar reaction with an unhindered substrate, and a negatively-charged nucleophile in a polar, aprotic solvent. When the inverse is used, e.g. hindered substrate in a nonpolar, protic solvent, it is expected that the reaction will be really slow. However, this is not true, as seen in an experimental setup. This is called an SN1 reaction, where first-order kinetics occur. In this experiment, a tertiary alcohol (hindered substrate) was used. Thus, the mechanism in this experiment is SN1, which stands for substitution, nucleophilic, unimolecular1.
CH3 HO CH3 CH3 H CH3 O H
+

HCl

CH3 CH3

Cl

(2)

The slow, rate-determining step for this mechanism is the loss of a water molecule from the oxonium ion (3)5.
H CH3 O H
+

CH3 CH3 C
+

Figure 2. A simple distillation setup Results and Discussion In the reactions of alkyl halides, nucleophilic substitution is one of the most widely occurring and versatile reactions in the field of organic chemistry. Nucleophilic substitution was first discovered on 1896 by a German chemist named Paul Walden. In this experiment, there are two mechanisms the reaction (1) may proceed to occur. It depends on the structure of R group. However, these two mechanisms both start by protonating the alcohol to produce an oxonium ion (2)5. There are two prominent types of nucleophilic substitution: SN2 and SN1. For the SN2 reaction, a single step reaction is observed with no intermediates occurring. An inversion

CH3

+H2O

(3)

CH3

CH3

After the formation of the carbocation (R+), it reacts rapidly with the chloride ion to form the alkyl halide (4)5.
CH3 C
+

CH3 CH3

+ Cl -

Cl

C CH3

CH3 (4)

CH3

However, only 80% of tert-butyl cations react with the chloride anion to produce the alkyl halide. The remaining 20% of cation react with water, which acts as a base. The water removes a proton from the carbocation to produce isobutylene, or 2-methylpropene in the following reaction (5)5.

Conclusion
H H O H

H H

CH3

H3O

+ H2C
CH3

CH3

(5)

CH3

This reaction may compete with the main reaction, and decrease the yield of tert-butyl chloride5. However, this can be minimized by having a low temperature in the setup and high concentration of the chloride of ions2. In the experiment, the hydrochloric acid was added in excess, and was placed in an ice bath beforehand to avoid the formation of isobutylene. In the actual experiment, only 1 mL of the tert-butyl chloride was collected. The expected yield of the experiment was 11.59 mL of tert-butyl chloride. Using these information, the percent yield was calculated as 8.63%. The low yield of the experiment may have been caused by different factors. The HCl used in the experiment may have not been cold or concentrated enough to completely inhibit the formation of isobutylene. Also, during the experiment, the organic layer turned orange when it was placed in the flask containing NaHCO3. This may have been caused by a dye, which may have affected the yield of the experiment. Also, the crude distillation setup may have also affected the yield of the experiment. For one, the water in the condenser was not cold, and the application of ice on the condenser may have not been enough to cool the water inside the condenser. The first few drops in the receiving flask were supposed to be discarded. However, due to difficulty in manipulation the setup, the amount of discarded liquid was around 2 mL. This may also have caused the decrease in yield of the experiment. Also, the instruments and glassware used in this experiment may have been inaccurate. Experimental conditions, such as temperature and humidity, may have also affected the results.

Overall, the objectives of the experiment were achieved. Tert-butyl chloride was synthesized from tert-butyl, and simple distillation was used as the purification method. However, only 1 mL of tert-butyl chloride was obtained, leading to an 8.63% yield. Still, the experiment can be considered successful, since the objectives were achieved. It is however recommended to use better equipment and glassware to improve the accuracy of the results. Also, other synthesis experiments involving an alkyl halide are also recommended. References (1) McMurry, J. Organic Chemistry, 8th ed; Brooks/Cole: Belmont, CA, 2012; pp. 344-345, 354-355, 372-394. (2) Swineheart, J.S. Organic Chemistry: An Experimental Approach; Meredith Corporation: New York, NY, 1969; pp. 160-162, 566. (3) Landgrebe, J.A. Theory and Practice in the Organic Laboratory with Microscale and Standard Scale Experiments; Brooks/Cole: Pacific Groove, CA, 1993; pp. 146-148. (4) Pavia, D.L. Introduction to Organic Laboratory Techniques: A Contemporary Approach; Saunders College: Philadelphia, PA, 1982; pp. 514-517. (5) Hart, H. Laboratory Manual: Organic Chemistry, A Short Course, 7th ed; Houghton Mifflin Company: Boston, MA, 1987; pp. 129-131.

Appendix Calculations ( ) ( ( ( ) ( ) ) ) ( ) ( ) ( ) ( )