Synthesis of an Alkyl Halide Joseph G.

Catiis Institute of Chemistry, University of the Philippines, Diliman, Quezon City Date Performed: December 5, 2013 Date Submitted: January 7, 2014 Abstract The purpose of this experiment is to verify the usefulness of using a hydrogen halide to synthesize an alkyl halide from an alcohol using distillation. The alcohol and hydrogen halide are reacted inside a separatory funnel and are subsequently separated. The organic layer is treated with NaHCO3 and anhydrous CaCl2 to remove excess HCl and moisture, respectively. In the end, although a small % yield of 17.3570% was obtained because of an accident, an accurate boiling point of 50.7C was obtained, verifying the usefulness of the experiment.

I. Introduction This experiment is aimed at synthesizing an alkyl halide (tert-butyl chloride) from an alcohol (tertbutyl alcohol) by reacting it with a hydrogen halide (hydrochloric acid). This happens via a unimolecular nucleophilic substitution reaction that will be discussed later. Also, as there is bound to be a side reaction, the experiment also includes purifying the product using simple distillation. The principle that governs the reaction that produces the alkyl halide is a kind of nucleophilic substitution reaction that is called an SN1 reaction. To summarize, the mechanism for the said reaction will lead to an overall reaction of

II. Methodology The experiment is divided into two parts: the synthesis part and the distillation part.

A. Synthesis Part First, 10 mL tert-butyl alcohol and 20 mL cold concentrated hydrochloric acid are measured. It is important to use an ice bath to assure that the HCl is cold. Next, the two reagents are transferred into a closed separatory funnel and swirled gently. Using an iron stand and an iron ring, the separatory funnel is allowed to settle undisturbed for 20 minutes so that the layers will separate. The stopcock of the separatory funnel should also be slightly open to facilitate the separation. Put a 50-mL Erlenmeyer flask below the set-up to be used later during the separation. For the separation of the layers to be facilitated, 3-5 mL of 6 M NaCl solution can be added into the mixture. Note however that adding too much will cause the formation of salt sands that might obstruct the mouth of the separatory funnel and prevent the separation. Determine which the organic layer is. The aqueous layer is where the NaCl solution goes, so the organic layer is the other layer. After determining this,

Figure 1: Overall unimolecular nucleophilic substitution reaction The purpose of this experiment is to verify if this reaction takes place by subsequently employing simple distillation to see if a distillate is obtained at the boiling point of tert-butyl chloride, and to what degree by solving for the percent yield.

separate the layers by slowly turning the knob of the separatory funnel and letting the liquid come out. Immediately close the knob when the interphase between the two layers reaches the bottom of the funnel. Then, the organic layer is to be transferred into a flask containing a small amount of solid NaHCO3. Once the mixture is swirled, it is then to be decanted into another flask. Next, a small amount of anhydrous CaCl2 must be added to the mixture. The mixture is then swirled and decanted again, now into a dry 25-mL round bottom flask. It is important that the flask be dry as this very flask will be used for the distillation. Also, put a few boiling chips for the distillation. B. Distillation Part Assemble the distillation set-up accordingly: Make sure that water enters below and leaves above the condenser. Also make sure that the joints are fitted snuggly as accidental disassembly will prove to be a disastrous and unfortunate event. Use a flask that is big enough such that the sample fills only 1/2 to 2/3 of its volume. Assemble the flasks and turn on the water supply and slowly heat the sample. Record the boiling point and adjust the heat such that the flow rate of the distillate is 2 drops per second. Discard the first milliliter of distillate and continue collecting the distillate at constant temperature (49-52C). Stop distilling before the sample dries. III. Results and Discussion When the experiment was performed, the following results are obtained tert-butyl alcohol tert-butyl chloride % Yield Initial amount: 7.75 g Theoretical Amount: 9.6791 g Actual Amount: 1.68 g 17.3570%

process. The joint connecting the flask to the rest of the distillation set-up was disconnected, causing the whole distillation process to terminate and leaving only a small amount of distillate. This could have been avoided if the joints were checked properly. As stated earlier, the result is caused by the mechanism of a unimolecular nucleophilic substitution reaction or an SN1 reaction. According to the said mechanism, the following reactions took place

Figure 2: First Step in the nucleophilic substitution First, the alcohol group is protonated by HCl.

Figure 3: Second Step in the nucleophilic substitution Then, spontaneous dissociation of the protonated alcohol occurs as a slow reaction.

Table 1: Summary of Key Results As it can be seen, the % yield is very small. This was caused by an accident during the distillation

Figure 4: Last Step in the nucleophilic substitution Lastly, the carbocation reacts with the chloride to produce the alkyl halide that is tert-butyl chloride.

For this mechanism to work, the procedures must be followed closely. The significance of different steps in the procedures will be discussed. Cold HCl is used in the reaction because a certain side product is likely to predominate at warm conditions. That product is 2-methylpropene. The proposed mechanism for the formation of 2methylpropene is an E1 elimination reaction or unimolecular elimination reaction.

already boiling so that they may adjust the heat source accordingly. A continuous heat flow is necessary because if the water is not continuously replaced, the evaporated tert-butyl chloride will not condense, diminishing the amount of distillate. Overall, the purity of the product cannot be assured because of the accident. If it were not for that, however, it can be assured because the first millilitre of distillate is discarded so that the distillate that is to be considered is the fraction that is garnered at constant temperature, which is 50.7C for this experiment. Aside from the distillation accident, there was also another accident, albeit less serious, that happened in the separation using the separatory funnel. ue to excessive addition of NaCl solution, salt sands formed and blocked the opening of the funnel, making it impossible to proceed with the separation. The experimenters had to improvise by using a stirring rod to get rid of the blockage. IV. Conclusion Given the data that are collected and the analyses at the discussions part, we can say that using a hydrogen halide to synthesize an alkyl halide from an alcohol is an effective method, given the closeness of the constant distilling temperature (50.7C) to the actual boiling point of tert-butyl chloride (51C). However, care must be observed, especially in distillation because a relatively structurally complicated set-up is involved, stressing the necessity to check for stability. The point for improvement for the experiment is determining exactly how much NaCl solution is just enough to avoid the formation of salt sands. V. References
[1]

Figure 5: First step of side reaction First, the dissociation will produce an intermediate carbocation.

Figure 6: Second step of side reaction Then, the bicarbonate will attack the hydrogen, producing 2-methylpropene, chloride and carbonic acid. In eliminating the excess HCl, solid NaHCO3 is used instead of an aqueous one because if an aqueous solution is used, it will add water to the mixture that is just separated from an aqueous layer. Anhydrous CaCl2 is added to the mixture to dry it because the mixture had to be as dry as possible. If there is excess water in the mixture, the distillation process will not run as smoothly. Boiling chips are added to give the experimenters a visual indication of when the sample is

McMurry, J. (2007) Organic Chemistry7th Edition, Cengage Learning 2008

[2]

McKenzie, C. 1967. Experimental Organic Chemistry. Prentice Hall, New Jersey.

[3]

Toss, D. 1979. Experimental Organic Chemistry. Prentice Hall, New Jearsey. VI. Appendices