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Abstract Alkyl halides can be prepared by the reaction of alcohols with hydrogen halides, HX (X can be Cl, Br or I). When treated with Cl, Br or I, alcohols undergo a nucleophilic substitution (SN) reaction. There are two kinds of SN reactions, the SN1 and SN2, which involves unimolecular and biomolecular respectively. In this experiment, alkyl halides were synthesized using tert-butyl alcohol and hydrochloric acid via SN1 method. SN1 mechanism involved protonation of the alcoholic oxygen, cleavage of the C-O bond to allow the loss of the good leaving group and give a carbocation intermediate and finally, attack of the chloride ion on the electrophilic carbocation to create an alkyl chloride. The insolubility of the alkyl halide in water allows the separation of it from the aqueous layer using a separatory funnel. The alkyl halide, then, were purified by a simple distillation apparatus using boiling point differences between the pure tert-butyl chloride and not. The experiment was deemed a success after a colorless tert-butyl chloride with a boiling point of 49.5° was gathered with a percent yield of 59.5% by the end of the experiment.
I. Introduction Alkyl halide is composed of an organic group and one or more halogen atoms that replaced hydrogen atoms. Therefore, it is another name for a halogen-substituted alkane. It can also be called haloalkanes or halogenoalkanes. Due to the presence of the halide ions, alkyl halides tend to be more polar than their alkane origin. Haloalkanes can be classified into primary, secondary or tertiary depending on the number of alkyl substituents that are attached in the C-X unit. Alkyl halides are widely used in both industry and agricultural aspects. One example is chlorofluorocarbon (CFC’s), which is a famous refrigerant and one of the factors that contribute to ozone depletion. In agriculture, alkyl halides are used as pesticides and fungicides. Because of the wide range of beneficial impacts of alkyl halides, a number of methods were developed for its systematic synthesis. The most common preparation method is by reacting alcohol with hydrogen halides in extremely acidic environments. In this production method, tertiary alcohols were recommended to be used because of the stability and relative
strength of the tertiary carbocation. Most primary and secondary carbocation tend to give unsatisfactory amount of product because of their lower stability and since most complex alcohols will be destroyed in the reaction by strong acids before any products are formed. Tertiary alcohols, however, will react properly with strong acids via simple displacement process. Halogens F, Cl, Br and I will readily substitute with the hydrogen atoms in the hydroxyl group of the tertiary alcohol to form alkyl halides via SN1 reactions. II. Methodology To begin the experiment, all materials and apparatus to be used were prepared. 10 mL of tert-butyl alcohol and 20-mL of cold concentrated HCl were put in a dry 30-mL separatory funnel. The mixture was swirled gently and was relieved by the internal pressure by slowly opening the stop cock from time to time. Then, it was allowed to stand undisturbed for 20 minutes and was added by 3-5mL of 6 M NaCl (sodium chloride) solution to give way to proper separation of the organic and non-organic layer. The layers were, then, separated by
The layer in which the water dissolves is the aqueous layer. A thermometer bulb was also placed just below the side arm of the distillation head. A few boiling chips were added to prevent sudden and overheating of the sample and then. HCl or HI. addition of 1-2 drops of water in each separated layers helps.5° The synthesis of alkyl halides from alcohol is done by a direct contact with a strong halogenic acid. HBr. In this experiment. For secondary alkyl halides. Results and Discussion By the end of the experiment. A continuous flow into the bottom of the condenser’s cooling jacket and out from the top was made sure to prevent buildup of pressure inside the condenser. In this experiment.5 amu 0. HF. . a simple distillation set-up was prepared as shown in Figure 1.5 mmol Colorless Insoluble 49. The sample was heated slowly to a gentle boil while the temperature rise rapidly then remains constant at the boiling point of the sample. III. The collected pure tert-butyl chloride was put in a 10-mL graduated cylinder and was cooled in an ice bath since the sample is highly volatile. which will be discarded into the waste acid bottle. The reaction of alcohol and halide ions reacted via nucleophilic substitution. until a minimum amount of the sample was left. was distilled.5% and properties of: Properties Mass Molecular Weight Density Mmol Color Solubility Boiling Point 5.77 g 92. which will probably result in the primary or secondary alcohol to be destroyed during the reaction even before the products are formed. Lastly. where most of the vapor condensed into liquid and finally.7°C. Synthesis of halides from tertiary alcohol is most recommended for this process because tertiary alcohols react immediately with reagents. the acid used was HCl (hydrochloric acid). however. the heat source was removed and the entire set-up was allowed to cool down before it was dismantled. Due to the fact that the boiling point of tert-butyl chloride is 50. The flame was adjusted in which the rate of the distillation occurs at 2 drops of distillate per second. the fraction that distilled at a constant temperature. wherein. the students were able to obtain tert-butyl chloride with calculated percent yield of 59.84 g/mL 92. The first 1 mL of the distillate was discarded. primary and secondary alcohols have longer reaction time. The mixture was decanted into another dry flask. Once the sample was placed inside the flask. was collected. This temperature will be recorded. only the fraction of the sample that boiled at 49-52°C was collected. To determine which the aqueous layer is. Tertiary alkyl halides consistently undergo SN1 pathway while primary and methyl alkyl halides use the SN2 pathway. The organic layer was transferred into a dry flask containing a small amount of NaHCO3 (sodium bicarbonate) and was swirled gently. the leaving group is attached to the sp3-hybridzed ion. When the sample stated to boil. A water bath was prepared to regulate the temperature of the set-up. In the distillation process. The collected filtrate was dried with a small amount of anhydrous CaCl2 (calcium chloride) to remove traces of water left in the crude product as well as unreacted alcohol then decanted into a dry 25-mL round bottom flask. The vapors and condensate passed through the side arm and into the condenser.discarding the aqueous layer. the mechanism for this transformation depends on the classification of the alkyl group bearing the leaving group. the product was put in a labeled vial and was submitted to the instructor. both pathways are possible. A round bottom flask of appropriate volume wherein the sample fills ½ to 2/3 of the volume was chosen. 2-3 pieces of tiny glass capillaries were added but it was made sure the liquid was not hot yet. The water flow through the condenser and the fitting of the glass joints were checked after the water supply was turned on. The constant temperature was the boiling point of the volatile component. on the other hand. dripped from the adapter into the receiving flask. However.
ion. During the reaction. For alcohols. which is tert-butyl alcohol due to the water present in the aqueous solution.5% yield at the end of the experiment. the OH-. on the electrophilic carbocation to form the neutral tert-butyl chloride. Following each step carefully and being familiar on each note about the procedure of the experiment proved to be helpful for gaining a relatively large percent yield. The students were able to gather a 59. sometimes. IV. Also. This will prevent superheating of the product and going to temperatures above their average boiling points without the actual boiling process. solid NaHCO3 neutralizes excess HCl adequately. some of the protonated form loses the water. when alcohol is treated with the strong acid. is protonated first. The next step in the reaction is the attack of the Cl. Based on the SN1 mechanism stated earlier. The sample product was also dried before the distillation process by anhydrous CaCl2 to remove traces of water and unreacted alcohol that can mess about with the boiling point and distillation set-up of the whole experiment. which is relatively far from the boiling point of the alkyl halide thus. For example. Hydrochloric acid was added in excess to be certain that the reaction will reach equilibrium towards the product and be able to form a reasonable amount of alkyl halide. This result to the OH. removal of it should be easy. some 2methylpropene can be formed as a byproduct by the reaction of the remaining H+ free hydride and intermediate carbocation before the reaction between the chloride anion and intermediate carbocation happens. which is considered the leaving group. To ensure the success of the experiment. This step is considered as a very fast and reversible process. Drying with CaCl2 before distillation is also given stress because without drying. It can be. which is considered the leaving group. in the aqueous solution. is protonated first to give an oxonium. solid NaHCO3 was used to remove extra H+ in the final aqueous product since use of aqueous NaHCO3 can lead to hydrolysis of the tertbutyl chloride back to its original form. In SN1 reaction. the key step is the loss of the leaving group to be able to form the carbocation ion. Use of boiling chips was also pointed to provide surfaces in which bubbles can form and ensure a constant and equal flow of heat to the sample. thus. the objectives of the experiment were achieved. which will be stabilized by forming a double bond (alkene) with the loss of proton at the second carbon. However. therefore. Conclusion By the end of the experiment. the OH-. preventing the build-up of pressure inside the condenser and giving possibility to a smooth flow of steam and good recovery of the vapor. it was stated to use cold hydrochloric acid to prevent isobutylene. (CH3)2C=CH2. displaced by the entering halide ion. formation and to make sure the synthesis of alkyl halide. Tert-butyl chloride was successfully synthesized from tert-butyl alcohol using HCL .tert-butyl alcohol is considered a tertiary alcohol thus it will proceed via SN1 pathway. resulting to the formation of the free carbonium ion. it was researched that 2-methylpropene boils at 6° degrees. The mixture of the alkyl halide and the 2-methylpropene can result to possible wrong gathered data about the purified sample. distillation would boil the halide with moisture which will also result to hydrolysis of the halide. During the distillation process. The importance of the continuous flow of water in the condenser during distillation was also given point to make certain that the condenser will be able to transfer the suppressed heat inside it due to the evaporation of water. However. a lot of notes about precaution were given.binding with H+ to form a water molecule and an intermediate carbocation.
Chang.as the hydrogen halide. the OH-. displaced by the entering halide ion. However. With the objectives acquired and results gained. A large amount of tert-butyl chloride was obtained resulting to a huge percent yield. 4. resulting to the formation of the free carbonium ion. V. How can it be removed during purification? Based on the SN1 mechanism stated earlier. 2006 ed. Why is it necessary to use cold concentrated HCl? Why is it added in excess? It is to prevent alkene formation and ensure synthesizing of alkyl halide. 3. E & et al (2009). United States of America: Wadsworth.. (For data sheet. some of the protonated form loses the water. which will be stabilized by forming a double bond (alkene) with the loss of proton at the second carbon. 5. Why is solid NaHCO3 used instead of aqueous NaHCO3? Solid NaHCO3 is preferably used to prevent hydrolysis of the tert-butyl chloride back to tert-butyl alcohol due to the water present. Quezon City. Give a mechanism for its production. Appendices Answers to Questions: 1. Chemistry: The Central Science 11th edition. R. 6. LTD. It is added in excess to make certain that the reaction will reach equilibrium (towards the products) and be able to form reasonable amount of alkyl halide. when alcohol is treated with the strong acid. the water evaporated (due to heating) will pass as a steam. Purification techniques were also mastered by hands-on work. References Brown. sometimes. If there is no continuous flow of water.) . It can be. please see attached paper. LeMay. Organic Chemistry Laboratory Manual. Discuss the importance of the continuous flow of water in the condenser during distillation. 2. Notes about distillation techniques were grasped and taken point of. therefore. Results such as properties of tert-butyl alcohol and tert-butyl chloride were also recorded. Chemistry Tenth Edition. (2002). The McGraw-Hill Companies.Philippine edition. In the condenser. 1221 Avenue of the Americas: New York McMurry. T.. VI. Explain why some 2-methylpropene can be formed in the reaction as a byproduct. Inc. the experiment is deemed as a success. J. Pearson Education South Asia PTE. Why must the crude alkyl halide product be dried carefully with anhydrous CaCl2 before distillation? Anhydrous CaCl2 is used to remove traces of water before distillation. which is considered the leaving group. H. (Philippine Representative Office).. is protonated first. University of the Philippines Diliman. (1984). What is the purpose of boiling chips? Pure samples tend to be superheated and go to temperatures above their average boiling points with actual boiling. the condenser will not be able to transfer the suppressed heat thus resulting to build-up of pressure inside the condenser and affecting the distillation process. Organic Chemistry. These boiling chips provide surfaces in which bubbles can form and ensure a constant and equal flow of heat to the sample.
Figure 1. Simple Distillation Set-up .
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