Synthesis of an Alkyl Halide

Co Soriano, John Clyde L. Institute of Biology, College of Science University of the Philippines, Diliman, Quezon City, Philippines
Date Submitted: Jan. 2, 2012

Abstract Alkyl Halides are made from the reaction of an alcohol with a hydrogen halide HX (where X is a halogen). The halogens I, Cl and Br undergo one of two types nucleophilic substitution, namely Sn1 and Sn2. Only those molecules that form extremely stable cations undergo SN1 mechanisms. The experiment involves the reaction of tert-butyl alcohol and HCl and the separation of the alkyl halide from water with the use of a separatory funnel. The alkyl halide was then purified using a simple distillation set-up (fig. 1). The researchers have found significant success from this experiment, as their purified tert-butyl chloride had a boiling point 51C of (the actual boiling of point of tert-butyl chloride is 50.7 C) and the percent yield was 61%.

Introduction Alkyl Halides, also known as haloalkanes or halogenoalkanes are composed of an organic group wherein one or more hydrogens have been replaced by halogens. They are, in general, colorless, odorless and hydrophobic. They are also more polar than their parent alkane due to the halogen substituent and a higher boiling point due to London dispersion forces within the carbon chains. They are widely used in industry, agriculture and pharmaceuticals. Examples of this are polyvinyl chloride (PVC), polytetrafluoroethene (Teflon), fluorocarbon anesthetics and many more. There are three types of Alkyl halides. In primary (1) alkyl halides, the carbon that carries the halogen atom is only attached to one other alkyl group. A secondary (2) alkyl halide has two attached carbon to the carbon that has the halogen. A tertiary alkyl halide (3) has three carbons attached to the carbon that has the halogen. They are also classified depending on the halogen attached. They are called organofluorine, organochlorine, organobromine and organoiodine compounds. Because of the uses and the benefits provided by alkyl halides, systematic techniques have been formulated and developed to

synthesize them. One common technique is the reaction of alcohol with hydrogen halide in extremely acidic environments. It is also important to yield a 3 alkyl halide because of the strong carbocation. Tertiary alcohols (like tert-butyl chloride) must be used. If it was first or second degree, the product would not be stable and would yield several different products. I, Cl and Br will react readily with tertiary alcohols while the presence of a Lewis acid like zinc chloride is required for reaction with primary and secondary alcohols (Organic Chemistry Laboratory Manual, 2008 ed.). Methodology For the experiment, the following materials were used: Tert-butyl alcohol Concentrated HCl Solid NaHCO3 Ice bath 30mL separatory funnel Distillation set-up 50 mL Erlenmeyer flask Thermometer Bunsen Burner Oil bath Rubber tubing CaCl2

10mL of tert-butyl alcohol and 20mL of concentrated HCl were gently mixed together in a separatory funnel. The mixture was then swirled, not shook to prevent sudden build-up of pressure. 3-5 mL 6M NaCl was added to facilitate separation. The solution was left to settle for 20 min. The funnel was opened from time to time to relieve pressure. After the separation, the aqueous layer was determined by adding a few drops of water and was discarded by letting the organic layer flow through the bottom of the funnel, leaving the water behind. The organic layer was transferred to a dry flask with a small amount of solid NaHCO3 and then it was decanted into another dry flash. CaCl2 was then added to absorb the remaining water. The collected tert-butyl chloride was distilled using a simple distillation set-up (fig. 1). The sample was gently heated to boiling as the thermometer was read constantly. Distillation is the process of purifying a substance by using the difference in the boiling points of the substance and the impurities. The water goes from the faucet into rubber tubing, into the lower opening of the condenser and out of the higher opening of the condenser. The tert-butyl chloride vapor goes up and into the condenser where it becomes liquid again. It is then collected at the receiving flask. The flame was adjusted so that the liquid fell at two drops per second. One must not distill to dryness. The substance purified should have a boiling point lower than the impurities for the set-up to work. Boiling chips were put to cushion the rise of bubbles and avoid splattering when boiling. The boiling point of tert-butyl chloride is between 49-52 C. The boiling point and percent yield of the tert-butyl chloride was determined. Results and Discussion The researchers have obtained a 61 percent yield after the experiment. Other findings were noted down in the chart below. Much of the product was lost due to deficiency of precision in separation and imperfections in the distillation set-up. Tert-butyl Chloride Molar mass 92.57 g/mol Density 0.84 g/cm3 Theoretical Yield 7.809 g Acutal Yield 4.7g

Percent Yield Color

61% Colorless

Percent yield = Theoretical Yield / Actual Yield x100 Tert-butyl chloride was formed from the reaction of tert-butyl alcohol and HCl. Looking at the mechanism, the electrophilic oxygen gains the proton of the hydrogen and detaches itself from the parent compound, forming water (fig. a). With the hydroxide group gone, an electrophilic carbocation intermediate is formed which attracts the electron of the chlorine (fig. b). The products are Tert-butyl chloride and water (fig. c) and the reaction is an Sn1 reaction. Mechanism:

fig. a

fig. b

fig. c HCl was added in excess to push the reaction toward the formation of products. It was cold and concentrated so that the alkyl halide would not be hydrolyzed into its alcohol again and so that isobutylene would not be formed. Layers were formed because of the difference of the polarity of tert-butyl (nonpolar) chloride and water. The organic layer was at the bottom. This was determined when the water dropped mixed with the aqueous layer, which was above. Tert-butyl alcohol is a tertiary alcohol therefore it had produced a stable alkyl halide. NaHCO3 was added to the tert-butyl chloride to remove addition H+ ions to avoid its hydrolysis. Drying with CaCl2 before distillation was done also to prevent hydrolysis. Boiling chips were used to ensure consistent flow of heat and to avoid splattering of bubbles.

Some 2-methylpropene may be formed as a minor product. Looking at the mechanism, when the carbocation intermediate is formed, the OH- ion would bind with the H+ form HCl. But sometimes the H+ binds to the carbocation but is makes itself more stable by forming a double bond (alkene). The result is 2methylpropane. Summary and Conclusion The reaction of tert-butyl alcohol and HCl produces tert-butyl chloride and water. It is an Sn1 reaction. Tert-butyl chloride has a boiling point of 50.7 C and therefore will evaporate first before water, 2-methylpropene and the impuritues. The researchers were successful in following all the procedures in the experiment and in synthesizing Tert-butyl chloride with a high purity from the reaction of tert-butanol and HCl. They were also successful in assembling and using a simple distillation set-up. A high percent yield of 61% was obtained at the end of the experiment. They were also able to observe closely and understand each of the steps of the experiment. The experiment was a success. References Conant, J. The Chemistry of Organic Compounds: A Years Course in Organic Chemistry. Maximillian Company: New York, 2001, pp. 23-24, 278-279. Fessenden, R. and Fessenden, J. The Basis of Organic Chemistry, 2nd edition, Allyn and Bacon Inc: Boston, 184, 225. http://www.cliffsnotes.com/study_guide/SN1versus-SN2-Reactions.topicArticleId23297,articleId-23256.html Organic Chemistry Lab Manual (2008), Institute of Chemistry: UP Diliman, 34-37. Schmid, G. Organic Chemistry, Mosby: Chicago, 172-173, 558-560.

Appendix 1. Why is it necessary to use cold concentrated HCl? Why is it added in excess? To prevent alkene formation and ensure synthesis of alkyl halide. It is added in excess to push the reaction forward to ensure formation of products. 2. Why is solid NaHCO3 used instead of aqueous NaHCO3? Solid NaHCO3 was used to pervert the hydrolysis of the tert-butyl chloride back to the tert-butyl alcohol. 3. Why must the crude alkyl halide product be dried carefully with anhydrous CaCl2 before distillation? It has to be dried carefully to ensure that no tert-butyl alcohol is left and to ensure that the no water will interfere with the distillation. 4. What is the purpose of boiling chips? Boiling chips are used to cushion the bubbles that violently rise up during boiling. The chips are used to avoid splattering of fluid. 5. Discuss the importance of the continuous flow of water in the condenser during distillation. As tert-butyl chloride vapor passes through the condenser, it is the role of the cold running water to absorb heat from the vapor for it to condense. If the water were not running, the water would increase in temperature, reducing its ability to absorb heat. If the water is not running, there will be less yield. 6. Explain why some 2-methylpropene can be formed in the reaction byproduct. Give a mechanism for its production. How can it be removed during purification? Sometimes, after the OH- has been protonated and detached, the resulting carbocation attracts the hydrogen instead of the halogen, forming a carbonium ion. It stabilized itself by forming a double bond with the loss of one hydrogen at the second carbon. 2-methylpropene is gas in room temperature and so it will just leave the container. Calculations: 10mL tert-butyl alcohol x 0.7809 g/mL = 7.809g (actual yield = 4.7g) 4.7g/7.809 x 100 = 61%