Synthesis of an Alkyl Halide Anjelika Mae L.

Marquez Department of Mining, Metallurgical and Materials Engineering, University of the Philippines, Diliman, Quezon City December 6, 2013 December 18, 2013 Abstract This experiment synthesized a tert-butyl chloride from tert-butyl alcohol by the addition of excess HCl. The reaction occurred was a SN1 reaction. Crude tert-butyl chloride was formed by the addition of HCl and tert-butanol that was swirled and formed layers that was separated. The collected organic layer was removed of trace compounds by the addition of anhydrous CaCl2 and solid NaHCO3 and was then purified through distillation. This experiment yielded 5.52 g of product and the theoretical yield was 9.75g therefore the percent yield is 56.65%.

I.

Introduction Alkyl halides are organic compounds containing at least one carbon and halogen bond where the halogen atom or atoms (X) are bonded to a sp3 orbital of an alkyl group (R). Halogen atoms are more electronegative compared to carbon atoms therefore the C-X bond is polarized where the X is the partially negative side and the C is the partially positive side. Alkyl halides are widely used in medical, industrial, and commercial applications. Examples are Chlordane, a pesticide; Freon- 12, a widely used refrigerant; and haloethane, an anesthetic. Organic compounds with halogens are rarely found in nature that is why alkyl halides are synthesized from other organic compound. Alkyl halides can be synthesized by (1) the electrophilic addition of HCl, HBr, or HI to alkenes (2) Addition of Cl2 or Br2 in the presence of heat or light via free radical mechanism. (3) The use of alcohol with HCl, HBr, or HI In this experiment, tert-butyl alcohol ((CH3)3COH) will be treated with concentrated hydrochloric acid (HCl) to produce tert-butyl chloride ((CH3)3CCl) that will be then purified by simple distillation. II. Methodology Place 10 mL tert-butyl alcohol and 20 mL cold concentrated HCl in a 30 ml separatory funnel. The mixture was swirled gently, and then the stopcock was opened once in a while to relieve the pressure. The mixture was left undisturbed for 20 minutes and was added with 3-5 mL of 6M NaCl solution to facilitate the formation of layers. When the layers form, the aqueous layer was discarded. The organic layer was transferred to a dry flask containing a small amount of NaHCO3. The mixture was swirled gently then decanted into another dry flask. The filtrate was dried with Calcium chloride (CaCl2) and was decanted into a dry 25 mL round bottom flask.

A simple distillation set-up was prepared. The water flowed into the bottom of the condensers cooling jacket and out from the top. The thermometer bulb was placed just below the side arm of the distillation head. A round bottom flask that can contain -2/3 of the samples volume was chosen, and a water bath was used to regulate the temperature. The sample and a few boiling chips was added first before distilling the crude tert-butyl chloride. The sample was heated slowly to a gentle boil. The temperature rapidly rose and remained constant only at the boiling point. The vapors and condensate passed through the side arm, into the condenser, the adapter, and into the receiving flask. The flame was adjusted so that the distillation would occur at a rate of 2 drops per second. The 1st 1 mL was discarded and the fraction that boiled at a constant temperature was collected. The heat source was removed when the sample started to boil. The setup was allowed to cool before it was dismantled. The pure tert-butyl chloride was collected in a 10 ml graduated cylinder that was placed in an ice bath. The fraction that boiled at 49-50oC was collected, put in a vial, and was submitted to the instructor. III. Results and Discussion The objective of this experiment was to synthesize tert-butyl chloride from tert-butyl alcohol by adding HCl to the alcohol as shown below.

Figure 1: Addition of HCl to tert-butyl alcohol The type of reaction that happened was a SN1 nucleophilic substitution that produced an alkyl halide and water because the alcohol is a tertiary alkyl group. This occurs only at basic or acidic conditions.

The first step is an acid-base reaction involving the weak base t-butanol and the strong acid HCl. The alcohol will be protonated to make a better leaving group -OH2 . An additional hydrogen is added while swirling the mixture of t-butanol and HCL. This is a very fast and reversible step.

amount of solid NaHCO3 . Solid NaHCO3 instead of aqueous NaHCO3 was used to prevent water from entering the mixture and prevent to prevent hydrolysis that would form an alcohol. NaHCO3 was added to remove excess acid in the mixture. NaHCO3 (s) + HCl (aq) CO2 (g) + H2O (l) + NaCl (aq) Anhydrous CaCl2 of a small amount was added to remove traced of water from the reaction between NaHCO3 and HCl. Again, anhydrous CaCl2 was used so that water would not be introduced in the mixture. CaCl2 can also remove traces of alcohol since Ca2+ can form many complexes with oxygen containg compounds. CaCl2 would only react with alcohol and water since it is insoluble in organic liquids. Simple distillation was used to purify the crude sample by eliminating solid impurities and to collect the the tert-butyl chloride at the temperature 50C since only pure tert-butyl compound will have a boiling point of 50C. The following data was collected from the experiment. t-butyl chloride Mass Molecular Weight Density 5.52 g 92.57 amu 0.84 g/mL 37.29 mmol Colorless Sparingly soluble 50C t-butyl alcohol 7.8086 g 74.12 amu 0.78 g/mL 105.35 mmol colorless soluble 83oC

Figure 2: Protonation of t-butanol The second step is the cleavage of the C-O bond allowing the loss of the leaving group OH2 therefore giving a carbocation intermediate. This is the slower step since it involves bind breaking which is an endothermic reaction.

Figure 3: Formation of the Carbocation In the last step, the nucleophilic chloride ion will attack the electrophilic carbocation creating the alkyl halide tert-butyl chloride

Figure 4: Attack of the nucleophilic ion This reaction will not yield a 100% pure tert-butyl chloride since not all molecules will react. Because of this, an alkene may form from the residual tert-butyl alcohol by an E1 elimination. To prevent the formation of an alkene, cold HCl was used. Also there was an of excess HCl because much chloride ions is need to act as the nucleophile that will attack the alcohol. The remaining HCl will not react since the tert-butyl alcohol is the limiting reagent. There was a separation of layers after the mixture was left undisturbed. The addition of NaCl made the separation faster because the NaCL increased the ionic strength of the polar forms. The NaCl reacted only with the aqueous layer because of the oxygen in the aqueous layer. This made the aqueous layer denser compared to the organic layer. After the aqueous layer was discarded, the organic layer was decanted into a flask containing a small

Mmol Color Solubility in water Boiling Point

Table 1: Experimental data of the alkyl halide synthesis The percent yield was calculated to be at 56.65%. Possible sources of error maybe because (a) some water may have entered the system by not using totally anhydrous CaCl2 (b) Trace alcohol was left leading to formation of other compounds like an isobutylene

IV. Conclusion The objective of being able to synthesize an alkyl halide from alcohols was achieved with a percent yield of 56. 65% thus the experiment is a success. The errors in this experiment may be lessened by the improvement of the reactants used. Make sure that the CaCl2 has zero amount of water, and check that the other reagents are not contaminated. Properly following the procedures would increase the percent yield of the experiment.

1 It is necessary to use concentrated HCl because the reaction needs a great amount of chloride ions and because the reaction needs an acidic medium to take place, and if you use hot HCl, alkenes will form. 2 Because if aqueous NaHCO3 is used, water will be once again introduced to the mixture. Water should be removed to prevent hydrolysis , thats why the aqueous layer was discarded before. 3 To prevent hydrolysis of the Alkyl halide (to an alcohol) during the distillation of the product. 4 Boiling chips are small porous things that trap air. It provides spaces so that bubbles of solvent can form. Boiling chips ensure even boiling and loss of solution due to boiling over. 5 If the water has no continuous flow, the water will just absorb the heat from the condenser until the water has the same temperature as the condenser therefore making it useless since the water will not absorb anymore heat from the condenser so the vapor will not cool and there will be no condensation. 6 If there is a residual alcohol left, it may react to form an alkene by E1 elimination. It can easily be removed because it has a low boiling point of only -6.85oC. This product would not really matter since in the experiment, the one that boils 49-52oC will be the only one collected

V. References Brown, T., LeMay, H, E & et al (2009). Chemistry: The Central Science 11th edition. Pearson Education South Asia PTE, LTD. (Philippine Representative Office),Philippine edition. Lawrence G., Organic and Biological Chemistry Laboratory Manual, Long Islang University, Brooklyn. McMurry, J. (1984). Organic Chemistry. United States of America: Wadsworth. Organic Chemistry Laboratory Manual. University of the Philippines Diliman, Quezon City. 2008 ed.

VI. Appendices Answers to question 1. Why is it necessary to use cold concentrated HCl? Why is it added in excess? Why is solid NaHCO3 used instead of aqueous NaHCO3? Why must the crude alkyl halide product be dried carefully with anhydrous CaCl2 before 4. 5. distillation? What is the purpose of boiling chips? Discuss the importance of the continuous flow of water in the condenser during distillation Explain why some 2-methylpropene can be formed in the reaction as a byproduct. Give a mechanism for its production. How can It be removed during purification?

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