SYNTHESIS OF AN ALKYL HALIDE

Anna Sophia M. Ebuen Department of Mining, Metallurgical and Materials Engineering, College of Engineering University of the Philippines, Diliman, Quezon City 1101 Philippines Date Performed: December 11, 2012; Date Submitted: January 8, 2013

Alkyl Halides are compounds derived from alkanes with a halogen included in it. It can be synthesized through the reaction of an alcohol and a hydrogen halide, thus the objective of the experiment. An important process contained in this experiment is the simple distillation wherein the purification of a compound is done. It is through from both the activity of evaporation and condensation that the process of distillation occurs. The purified compound is the product that the objectives aim in which the result was ## grams of tert-butyl compound. The end result was colorless in appearance and has a boiling point of ## degrees Celsius. With a ## percent recovery, there is an slight deviation of the experimental value to the theoretical because of an imperfect set-up and other various factors that contributed to inaccuracy of the data.

INTRODUCTION Alkyl Halides (also called haloalkanes) are compounds with a halogen atom bonded to a saturated sp3-hybridized carbon atom [1]. Being colorless, relatively odorless and hydrophobic (nonpolar), it generally resembles the parent alkanes. Most of the alkyl halides are artificially produced, thus there are several methods for preparing alkyl halides. The following are the reaction of alkanes with chlorine in the presence of sunlight (chlorination), another is the addition reaction of alkenes and hydrogen halides in which hydrohalogenation takes place, and last the reaction of alcohol with compounds such as hydrogen halides in order to yield an alkyl halide.

In the experiment done, a tert-butyl alcohol (tertiary alcohol) was used to react with a concentrated hydrochloric acid in order to synthesize a tert-butyl chloride. An SN1 (nucleophilic substitution) reaction took place wherein a spontaneous loss of a leaving group occurs which gives a carbocation intermediate then reacts with a nucleophile in the second step to yield the substitution product [1]. The more stable the carbocation intermediate, the faster the SN1 reaction is. This mechanism explains why a tertiary alcohol reacts more rapidly than the primary or secondary. The process of simple distillation is used to purify and eliminate the solid impurities in the mixture to yield the desired result, the tert-butyl chloride.

EXPERIMENTAL DETAILS In a 30-ml separatory funnel, a 10 ml tert-butyl alcohol and a 20 ml cold concentrated hydrochloric acid (HCl) were added. The mixture was swirled gently (dont shake) and from time to time the stopcock of the funnel was being slowly opened to relieve the internal pressure that is being formed. Subsequently, it was left undisturbed for 20 minutes so the partition of layers in the mixture will be visible. A few drops of distilled water (H2O) were added to determine the aqueous layer in which they will dissolve. The aqueous layer must be discarded while the organic layer was transferred into a dry flask which contains a small amount of sodium bicarbonate (NaHCO3). The solution was first swirled gently and then decanted into another dry flask. Afterwards, the collected filtrate was dried with a small amount of anhydrous calcium chloride (CaCl2) so that it will remove the water and unreacted alcohol left. It was decanted into a dry 25-ml round bottom flask with a few pieces of boiling chips in it and subsequently the crude tert-butyl chloride was distilled. The simple distillation set-up was prepared as shown in Figure1 in mind.

The water flowed to the bottom of the condensers cooling jacket and out to the top, while the thermometer bulb was placed below the side arm of the distillation head. Two beakers were used to contain water and oil bath separately. The glass joints were checked whether they were assembled well and the water supply was turned on to check the water flow through the condenser. The sample was slowly heated to a gentle boil wherein after some time the boiling point was recorded. Then the flame was adjusted so that the distillation occurs at a rate of 2 drops distillate per second. The first 1 ml of distillate was discarded whereas the one that distils at constant temperature was collected (boiling point). The heat source was removed when the sample to boil and the whole set-up was cooled up before dismantling it. The now pure tert-butyl chloride was collected in a 10-ml graduated cylinder cooled in an ice bath. The product was then submitted in a labelled vial to the instructor.

RESULTS AND DISCUSSION The main objective of the experiment is to synthesize a tert-butyl chloride from an alcohol and a hydrogen halide.

Figure2. Reaction Equation [1] The general mechanism in the experiment done is an SN1 (nucleophilic substitution) reaction which happens only on tertiary substrates and under neutral or acidic conditions. Tert-butyl alcohol, being a tertiary

Figure1. Simple Distillation Set-up

alcohol and HCl being an acid satisfy both the condition. SN1 reaction occurs by spontaneous loss of the leaving group before the incoming nucleophile approaches [1]. Initially, it is the rate-limiting step which starts the reaction, wherein it is dependent on the leaving group and the organic substrate. In this process, the bond to a leaving group (most stable anion) is broken which leads to the formation of the carbocation intermediate.

Figure6. Reactivity of Leaving Groups[1] Then, the next step is the dissociation of tertbutyloxonium ion in which the water leaves the protonated tert-butyl alcohol becoming a tert-butyl cation.

Figure3. Formation of a Carbocation Then, the next step is the interaction of the nucleophile with the carbocation intermediate to yield a product.

Figure7. Formation of Tert-butyl Cation And finally, the last step is attachment of the chloride ion to the cation becoming a tertbutyl chloride.

Figure4. Interaction of Nu- with Carbocation In the synthesis of a tert-butyl chloride, the mechanism is divided into three steps: First is the proton transfer from HCl to the tert-butyl alcohol.

Figure8. Attachment of Cl- to Cation In the experiment proper, a specifically cold concentrated HCl was used to react with the tert-butyl alcohol. The E1 (elimination) and SN1 reactions normally occur together whenever an alkyl halide is treated in a hydroxylic solvent with a nonbasic nucleophile, thus the best E1 substrates are also the best SN1 substrates [1]. Though with a hot HCl the process may lead to dehydration through the E1 mechanism, therefore a cold HCl will prevent alkenes from forming. The amount of product is determined by the amount of limiting reactant [2], in which the experiments limiting reactant is the tert3

Figure5. Protonation of Alcohol It is due to the fact that a hydroxide ion is not a good leaving group based on its reactivity. However, if one additional hydrogen atom is added water is formed which is more stable and favourable in the activity.

butyl alcohol. The acid can be added in excess because the chloride ions take the role of the nucleophile which attacks the alcohol. Putting both the tert-butyl alcohol and the hydrochloric acid in the separatory funnel resulted for the separation of layers, both organic and aqueous. It was determined by adding drops of water that the organic layer is at the top while the aqueous layer is below it. The organic layer has a density close to 0.8 and the aqueous layer (saturated aqueous sodium chloride solution) has a density of about 1.2 [3]. Afterwards, the organic layer was transferred in another dry flask and has been added with a solid NaHCO3. A solid NaHCO3 was used such that no water will be left since it might stop the reaction. In each experiment, the longer the product remains in contact with water or an aqueous NaHCO3, the greater the risk that the product will decompose that may lead to analytical errors [4]. Subsequently, a filtrate was collected, dried and was added with an anhydrous CaCl2, a drying agent. It is added to remove the traces of water and unreacted alcohol left in the dried organic filtrate to ensure that it is pure. The chemical reaction of anhydrous calcium chloride with water: CaCl (s) + H2O (l) --> CaCl.nH2O (s) Then, it was decanted into a round bottom flask with a few pieces of boiling chips. Its purpose is to provide surfaces so that bubbles can form as it boils as the temperature rises. Without the use of boiling chips, it can lead to a sudden formation of large gas bubbles which can lead to bumping. This can cause the liquid to splash over in the condenser which would produce an impure product. Afterwards, the crude tert-butyl chloride was distilled. Distillation is a technique that is used to purify a mixture of

liquids (eliminate solid impurities) and through this process, the boiling point of a pure liquid can also be determined. The boiling point of a pure organic liquid is a physical property of that liquid. It is defined as the temperature at which the vapor pressure of the liquid exactly equals the pressure exerted on it [5]. A continuous flow of water through the condenser is important in order for the two process of distillation to occur, evaporation and condensation. If there is an irregular water flow, a possibility that may happen is that all the liquid which evaporated in gaseous form wont be able to be condensed back in liquid form thus resulting for a poor recovery. It is known that tert-butyl chloride is the result of the experiment, however 2methylpropene can also be formed as a byproduct. This can happen if during the SN1 mechanism, the protonated ion loses the water which resulted to the formation of a free carbonium ion which will be stabilized by forming an alkene with the loss of proton at the second carbon. According to some research, this 2-methylpropene boils at 6 degrees which can be removed easily due to the vast difference of boiling point between the two [6]. By the end of the experiment, it was able to accomplish the desired objective which is to synthesize a tert-butyl chloride. Accordingly, the obtained results are: Table1. Properties of tert-butyl alcohol Weight 7.80 g Density 0.780 g/ml Molecular Weight 74.14 g/mol Mmol 105.21mmol Color colorless/ clear Solubility in Water soluble Boiling Point

With the equation in mind,

properties

above,

this

REFERENCES [1] McMurry, J. Fundamentals of Organic Chemistry, 7th ed.; Brooks/Cole: USA, 2011; pp 225, 234-237 [2] Whitten, K.; Davis, R.; Peck, L.; Stanley, G. General Chemistry, 7th ed.; Brooks/Cole: USA; pp 97 [3] Synthesis of Alkyl Halide http://orgchem.colorado.edu/labquizzes/alkhal /alkhalquizans.html [4] Pavia, D. Introduction to Organic Laboratory Techniques: A Small Scale Approach; Brooks/Cole: USA, 2005; pp 173 [5] Simple Distillation http://www.wellesley.edu/Chemistry/chem211 lab/Orgo_Lab_Manual/Appendix/Techniques/ SimpleDistill/simple_distillation_n.html [6] Nadura, R. R. Synthesis of an Alkyl Halide. 2010. Retrieved from http://www.scribd.com/doc/48973364/formalreport#download

the tert-butyl alcohol as the limiting reactant and the result of the experiment, it can be concluded that tert-butyl chloride has the following properties: Table2. Properties of tert-butyl alcohol Volume in grams Mmol 105.21mmol Theoretical yield 9.74g Color colorless Solubility in Water insoluble Boiling Point

Following the procedures diligently and also keeping in mind the important notes, the outcome of the experiment has a percent yield of and the boiling point.

CONCLUSION With the completion of the experiment, the objective (synthesis of alkyl halide) was achieved with a percentage yield of #% and the boiling point... With the process of simple distillation being performed, students were able to have a grasp of the process which would be a great help in the succeeding experiments. Even though the setup and the process are not completely ideal that it may incur various errors, they are really inevitable because they are a part of experimentation. However, it is best to reduce these errors for the improvement of the experiment. This can be done by properly cleaning the apparatus, handling the reagents, and following the procedures carefully in order to increase the percentage yield of the experiment.

APPENDIX A. Calculations Weight of t-buOH:

= 0.780

g x 10ml ml

=7.80g t-buOH

Molecular weight of t-buOH:

= 4(12.02) + 10(1.01) + 16 =74.14 g/mol t-buOH

Mmol of t-buOH:
=7.80g (

1mol 1000mmol ) ( ) 74 .14 g 1mol

=105.21mmol t-buOH

Mmol of t-butylchloride:
==105.21mmol t-buOH (

1mmol t butylchloride ) 1mmol t buOH

=105.21mmol t-butylchloride

Theoretical yield of t-butylchloride

=105.21 mmol t-butylchloride ( =9.74g t-butylchloride

1mol 92.57 g )( ) 1000mmol mol

Percent Yield
=

actual x100 theoretical

=###

B.

Guide Questions used Why is it necessary to use cold concentrated HCl? Why is it added in excess? Why is solid NaHCO3 used instead of the aqueous one? Why must the crude alkyl halide product be dried with anhydrous CaCl2 before distillation? What is the purpose of boiling chips? Discuss the importance of continuous flow of water in the condenser during distillation Explain why some 2-methylpropene can be formed in the reaction as a byproduct. How can it be removed during purification? Data Sheet (attached)

C.