Synthesis of an Alkyl Halide Gladys Ericka D.

Galang Institute of Chemistry, University of the Philippines, Diliman, Quezon City December 5, 2013 January 7, 2014 Abstract The objective of this experiment is to be able to successfully synthesize tert-butyl chloride from the reaction of tert-butyl alcohol and cold concentrated hydrochloric acid. Afterwards, the collected synthesized alkyl halide is to be distilled using a set-up to set it apart from impurities. The experiment conducted the synthesis with 7.89 g 0.18 mmol tert-butyl alcohol and ended with an 8.65 g 0.092 mmol alkyl halide. The experiment yielded 2.5 mL of distilled tert-butyl chloride from the given 10 mL of tert-butyl alcohol giving the experiment a 25% yield. I. Introduction Alkyl halides or Haloalkanes, are any organic groups, most of the time alkanes, that include one or more halogen groups instead of hydrogen atoms. Because the halogen is more electronegative, the carbon-halogen bond becomes polarized, the carbon and halogen is partially positive and partially negative respectively. The boiling point of alkyl halides are higher than those of alkanes even with the same number of carbons because of its partial charges and also the larger surface area created by the halogen attached to the compound. The boiling point increases as the one goes down the periodic table following the trend of increasing polarizability of halogens. Alkyl halides are insoluble in water, unlike alcohol which is soluble in all proportions. Alkyl fluorides and chlorides are less dense and alkyl bromides and iodides more dense than water. The compounds mixed in water will create layers over or under water depending on their density. Alkyl halides are classified into three groups depending on the classification of the carbon that holds the halogen functional group. Primary alkyl halides are attached to primary carbons with RCH2G configuration, G being the functional group, secondary alkyl halides to secondary carbons, R2CHG and tertiary alkyl halides to tertiary carbons R3GH. Tertiary alkyl halides are found to be most reactive and primary to be the least. Alkyl halides are used in various ways. They can be used as solvents for organic reactions, even for stains on clothes, and air-conditioning (chlorofluorocarbons and hydrochlorofluorocarbons). Alkyl halides are also used for drugs and treatments for certain diseases, and increase in crop yield. Alkyl halides are synthesized using elimination and substitution reactions. A common method of alkyl halide synthesis is the replacement of a hydroxyl group of an alcohol by a halogen on treatment with a hydrogen halide as it used in this experiment. II. Methodology The experiment is divided into two parts: the synthesis of tert-butyl chloride and the distillation of the product of the first part. Tert-butyl chloride was synthesized from tert-butyl alcohol. 10 mL of the alcohol was placed in a 10 mL separatory funnel. 20 ml of cold concentrated HCL was added. The HCL had to be cold to prevent alkyl formation and to ensure that alkyl halide will be synthesized. To make sure that the reaction will reach equilibrium and be able to form a good amount of the alkyl halide, the concentrated HCL was added in excess. The solution was swirled in the separatory funnel. The funnel did not have a stopcock so the experiment continued with only the swirling of the solution. 5 mL of 6 M NaCl was added to facilitate the separation of the aqueous and organic layers of the solution. It was left to stand for 20 minutes while the distillation part was being set up. After 20 minutes, the solution was had two separate layers. The layers were determined to be organic or otherwise by dropping water into the solution. The layer that dissolved the water was aqueous and was discarded from the solution. The organic layer was transferred to a dry flask containing a small amount of solid NaHCO3. Solid was used instead of aqueous NaHCO3 to prevent the synthesized tert-butyl chloride from hydrolysing back to tert-butyl alcohol. The solution was swirled and decanted into another dry flask. The filtrate was collected and dried with a small amount of anhydrous CaCl2. Anhydrous CaCl2 removes traces of and unreacted alcohol from the solution. A few boiling chips of were added to the

solution after it was decanted to a dry, 25 mL round bottom flask. The chips were boiled since pure samples tend to go temperatures above their boiling points. The chips cushion the bubbles that form and ensure a constant heat flow in the reaction. The distillation setup is as follows:

This step is the Bronsted acid-base reaction. Hydrochloric acid which acts as a proton donor, reacts with tert-butyl alchohol which acts as the proton acceptor. This reaction leads to the protonation of the tert-butyl alcohol. This forms a alkyloxonium ion as the conjugate base of the alcohol.

Figure 1. Distillation Set-up Instead of round bottom flask to catch the distilled alkyl halide, the students used a small graduated cylinder. The sample was placed on the flask on the left, and was constantly heated by a slowly boiling bath. The flame was adjusted until there is a constant rate of 2 drops distillate per second. The setup was allowed to cool before dismantling. All aqueous solutions were disposed by diluting them before pouring them into the sink. Organic compounds were disposed into their appropriate waste containers. III. Results and Discussions After the experiment has been concluded, the students gathered the following results: Properties T-B alcohol T-B chloride Color colorless colorless Sol in H2O soluble insoluble Boiling point 82 C 50.7 C Table 1. Results Collected The collected amount of tert-butyl alcohol was 2.5 mL in contrast to the theoretical yield of 10 mL giving a 25% yield. The reaction between tert-butyl alcohol and concentrated hydrochloric acid is a substitution reaction. (1) (CH3)3COH + HCL (CH3)3CCl + H2O

Then this alkyloxonium ion, the tert-butyloxonium ion which was formed as an intermediate dissociates into a molecule of water and a carbocation which contains a positively charged carbon. The third part of the mechanism is the reaction of the carbocation intermediate with the chloride ion to form the tert-butyl chloride.

The tert-butyl chloride gathered from the reaction is not pure considering other samples involved so it is distilled. The compounds boiling point is 50.7 C so the impurities evaporated from the solution and only the tert-butyl chloride condensed back into liquid form giving us 2.5 mL of the distilled product. The low percent yield from the distillation process reveals that there might more impurities present in the sample than the acid of the alcohol before the reaction. It may also be possible that there are unreacted reagents in the solution. Another possibility is the formation of 2-methylpropene that evaporated during the distillation. Given the 10 mL alcohol, its density and molecular weight, the students found that the mass of the alcohol was 7.89 g with 0.18 mmol and the alkyl halide to be 8.65 g and 0.092 mmol. IV. Conclusion The reaction of tert-butyl alcohol and concentrated hydrochloric acid forms tert-butyl chloride and water. The experiment conducted produced tert-butyl chloride with a 25% yield.

V. References Guch, I., Wayman K. The Complete Idiots Guide to Organic Chemistry. Penguin Group, New York 2007, pp. 129-147 Carey, F., Organic Chemistry 4th Ed. The McGrawHill Companies, Inc., US. 2000 Clayden J., et al, Organic Chemistry, Manchester University, 2000 Conant, J. The Chemistry of Organic Compounds: A Years Course in Organic Chemistry. Maximillian Company: New York, 2001, pp. 2324, 278-279 VI. Appendices List of Figures and Tables Figure 1. Distillation Set-Up Table 1. Results collected

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