Synthesis of an Alkyl Halide

Iris Charmaine Cruz Olaso Institute of Chemistry, University of the Philippines, Diliman, Quezon City 1101 Philippines Date Performed: July 9, 2013; Date Submitted: July 18, 2013

Alkyl halides are compounds with a halogen attached to the alkyl group. Because of the characteristic of an alkyl halide, it is being used in the industry in several ways. Hence, synthesizing these compounds must be done. One of the most common ways of synthesizing these compounds is by reacting alcohols with highly acidic substances using the mechanism of nucleophilic addition. In this experiment, tert-butyl chloride was mixed with hydrochloric acid in separatory funnel to synthesize tert-butyl chloride. Then, purification process was done using distillation method. A yield of 10% was obtained in this experiment. Introduction One of the functional groups in organic chemistry is the alkyl halides. Alkyl halides are organic compounds with a halogen atom bonded to a saturated sp3-hybridized carbon atom.[1] Given that halogen atoms are more electronegative than carbon atoms, the C-Hal bond is polarized in such a way that the carbon is partially positive and the halogen ion is partially negative.[4] Because of this, alkyl halides are also called halogen-substituted alkanes. Haloalkanes or halogenoalkanes are some other names for this compound. Due to its several industrial uses (e.g. chlorofluorocarbons (CFCs) being used in refrigerators and air-conditioners, anesthetics, pesticides), scientists developed several ways to readily synthesize alkyl halides. The most common method used to synthesize the alkyl halides is from alcohols treated with an acid (e.g. HCl, HBr or HI). Tertiary alcohols, R3COH, is widely used because of its relative stability and strength of the carbocation as compared to the primary and secondary alcohols. In this experiment, using tert-butyl alcohol treated with HCl as the hydrogen halide, tert-butyl chloride is synthesized. HCl was used since it reacts readily with tertiary alcohols. The product was then purified using the process of distillation. Experimental Details After the preparation of materials and apparatus to be used, 10 mL of tert-butyl alcohol and 20 mL of cold concentrated HCl was combined in a dry 30-mL separatory funnel. The mixture was swirled gently. Afterwards, 3-5 mL of sodium chloride was added. The solution was then allowed to settle for 20 minutes. After the two layers formed, the aqueous layer was discarded to separate the layers. In order to know which is the organic layer, 1 to 2 drops of distilled water was added. The layer in which the water dissolved is the aqueous layer. The separated organic layer was then transferred into a dry flask with a small amount of solid NaHCO3. The mixture was swirled gently then decanted into another 1

flask. The collected filtrate was allowed to dry with a small amount of CaCl2 to remove traces of water left in the crude product. This was then decanted into a dry round bottom flask. A few boiling chips were then added and the crude product was distilled. A simple distillation set-up was prepared. It was made sure that the water could flow into the bottom of the condensers cooling jacket and out from the tom and the bulb of a thermometer was placed below the side arm of the distillation head. Two round flasks are chosen wherein the sample shall be placed. Boiling chips were then added; take note that it should not be added to a hot liquid. The water supply was then turned on. The water flow must be checked and must be adjusted if there is a problem.

Afterwards, it was placed into a vial then was submitted to the instructor. Results and Discussions In this experiment, the synthesis of tert-butyl chloride was possible by the reaction of alcohol, tert-butyl alcohol with a halogenic acid hydrochloric acid. Tert-butyl alcohol was used since it is relatively stable and requires less reaction time and will most probably produce the results desired.[1] Cold HCl was used in this experiment to prevent alkene formation, in this case isobutylene to ensure the production of an alkyl halide.[1] The reaction of the alcohol and the halide ions is facilitated by nucleophilic substitution. In this case, the substrate is unimolecular and is a tertiary alkyl halide, thus it will undergo the first pathway.[3] In the first pathway, formation of a carbocation is possible by a group leaving. In this case, since alcohol was used, the group that will leave is OH- group. Once the OHgroup is protonated, an intermediate is formed which is the oxonium ion.[5]

Figure 1. Distillation Set-up[2] The flask containing the organic layer was heated while the other was placed in an ice bath. Slowly, the sample was heated and allowed to boil. The boiling point was then recorded. The vapors and condensates passed through the side arm then into the condenser and condense then will drop from the adapter to the receiving flask. The first 1 mL collected was then discarded and the fraction that boiled at 49-52 was then collected then cooled in an ice bath.

Figure 2. Protonation of OH- group[5] Afterwards, the halide will attack on the planar carbocation. Thus producing a neutral tert-butyl chloride. [5 ]

crude tert-butyl chloride and the product to be produced is pure tert-butyl chloride. In the distillation process, the heat must be evenly spread out to the sample, thus the addition of the boiling chips was done. Furthermore, this was done in order to prevent superheating resulting to temperatures greater than the theoretical boiling point which is 50.7. Note that, we allowed continuous water flow while the process is going on so that the condenser can successfully transfer suppressed heat and also release built-up pressure to produce better results. Note that, some 2-methylpropene may be formed in the reaction as a byproduct. As discussed earlier, the OH- group, is protonated first in the reaction. Thus, it may be displaced by the halide ion attacking. After the distillation process, a volume of 1 mL of tert-butyl chloride was obtained. Since theoretical yield was 10 mL, the percent yeield was only 10%. Conclusion Some reagents were added in order to attain better results before purifying the tertbutyl chloride. One of which is the solid NaHCO3 to remove extra H+ ions in the final aqueous product. Aqueous NaHCO3 was not used because it can lead to a hydrolysis of the product to its original form. Also, the solid sodium bicarbonate was used since can neutralize HCl very well. Another reagent was the anhydrous CCl2 which was used to dry the crude product. This was added in order to remove all traces of water and unreacted alcohol. After obtaining neutral tert-butyl chloride, the solution was then purified using the distillation process. Distillation was done in the experiment because the initial product is The objective of this experiment was obtained. The synthesis of tert-butyl chloride from tert-butyl alcohol treated with concentrated hydrochloric acid was done. A very low percentage yield of 10% was obtained This may be because of too much discarded product and failed distillation set-up. Therefore, it is recommended that more careful distillation set-up must be done. References [1] McMurry, J. Organic Chemistry, 8th Ed; Brooks/Cole; USA, 2012; pp. 344-345, 354355, 385-389. [2] Zubrick. J. The Organic Chem Lab Survival Manual, 4th Ed; 1997. Chapter 20: Distillation for Dummies. Retrieved July 18, 3

Figure 3. Production of tert-butyl chloride[5]

Presented in the table below are the different properties of tert-butyl chloride and tert-butyl alcohol. Table 2.1. Tert-butyl alcohol vs. Tert-butyl chloride Properties Mass MW Density Mmol Color Solubility BP Tert-butyl alcohol 7.85 g 74.12g 0.785 g/mL 108.41 mmol Clear Soluble 83 Tert-butyl chloride 3.78 g 92.57 g 0.84 g 40.83 mmol Clear Sparingly sol. 50.7

2013. http://www.erowid.org/archive/rhodium/chemi stry/equipment/distillation4dummies.html#. [3] Sweeting, L. Synthesis of Alkyl Halides. 1997. Retrieved on July 18, 2013 from http://pages.towson.edu/ladon/orgrxs/halide/ha lidesy.htm. [4] Rutgers-Camden. Alkyl Halides. Retrieved on July 18, 2013 from `http://crab.rutgers.edu/~alroche/Ch06.pdf. [5] University of Western Ontario. Preparation and Reactivity of Alkyl Halides. Retrieved on July 18 ,2013 from http://instruct.uwo.ca/chemistry/283g/labs/Exp eriment%201/2283-exp1.pdf.