Experiment 8: Markovnikov Addition of HBr to 1-Hexene

Aim:
1. To investigate the regiochemisty of ionic addition of hydrogen halide by reacting HBr with 1hexene, and subsequently to ascertain whether the addition conforms to Markovnikovs rule. To investigate the presence of 2-bromohexane in the product by noting the relative rates of reaction of the product in AgNO3/Ethanol test and NaI/Acetone Test. Discussion and Conclusion P1: With justification from Table 1 and Table 2, all proposed hypotheses were Data and Analysis: proven invalid. Referring to Table 2(a) , hypotheses 2 was incorrect for the Table 1: The first fraction containing solvent and unreacted 1-hexene was removed over a time taken for white precipitate to form was longer than had expected. range of room temperature to 80oC before collecting the product from 80oC onwards. All Referring to Table 2(b) , hypotheses 3 was proven incorrect when the time observation was observed and recorded. taken for white precipitate to form was drastically shorter than had expected. Finally, hypothesis 1 was invalid for the product collected from Process Observation Interpretation 80oC onwards was not 2-bromohexane. This was clearly proven by the Simple Distillate was collected from It may seem as if 2-bromohexane has confirmation test which failed as well. In conclusion, 2-bromohexane was not distillation of temperature of 80oC onwards been successfully formed. However, successfully synthesized and this synthesis did not adhere to Markovnikovs crude when crude product further confirmation test proved rule. Discussion and Conclusion P2: product underwent simple distillation. otherwise. Theoretical Result: 2-bromohexane ( Markovnikovs Rule) Experimental Result: Confirmation test results bore a storng resemblance to that of a 1o alkyl halide. Hence, the possible product formed was 1Table 2: The reactivity of the product towards the confirmation test was based on the bromohexane. relative time taken for white precipitate to appear. All observations were recorded Sources of error: and accounted for by interpretation of result. Firstly, the distillate vapor was not cooled effectively. When the Test Observation Interpretation temperature of the system hit about 90oC, the overwhelming amount of white vapors of distillate was not cooled completely by the condenser, (a)AgNO3/ A white The product did not contain 2-bromohexane. causing them to be lodged in the vacuum adapter. Cooling had to be done Ethanol precipitate(AgBr) was Ag/NO3 test is an SN1 reaction. The relatively poorly by wrapping the adapter with cold cloth. This ineffective cooling Test observed 40 seconds low reaction rate indicated that the product might have caused any 2-bromohexane to not be condensed, decreasing any after ethanolic AgNO3 contained 1-bromohexane instead of 2chances of obtaining the desired product. Secondly, the temperature of the solution was added to bromohexane which would show a higher system shot up to 120oC from time to time, causing any unwanted side the product. reactivity otherwise. products and solvents to be distilled as well. (b) NaI/ A white precipitate The product did not contain 2-bromohexane. Discussion and Conclusion P3: Acetone (NaBr) was observed NaI/Acetone test is an SN2 reaction. The 1. Markovnikovs Rule Test almost instantaneously relatively high reaction rate indicated that the This rule states that the hydrogen will add to the carbon of the C=C bond after NaI in acetone product contained 1-bromohexane instead of that already has the most number of hydrogen. This also forms the more solution was added to 2-bromohexane which would have an stable carbocations(2o/3o) which has the lower activation of free energy. the product. otherwise lower reactivity. Hence, addition of HBr to 1-hexene will give 2-bromohexane.(8.2A, 8.2B, Organic Chemistry, Solomons 10th ed). However, this was not observed in this experiment for Anti-Markovnikov took charge of synthesis and gave 1bromohexane. Anti-markovnikov involves formation of radical inermediate Calculations: instead of carbocation. (10.9,Organic Chemistry, Solomons 10th ed). 2. SN2 reaction of NaI/Acetone Test Mass of 25-ml receiver flask = 28.50g Being an SN2 reaction, NaI/acetone test is favored by unhindered Mass of 25ml receiver flask + product = 31.64g substrate with good leaving group that is a weak base, and a weak base Mass of product = 31.64-28.50 = 3.14g nucleophile such as iodide ion. In addition, polar aprotic solvent also Mass of 1-hexene = volume x density= 6.00 x 0.67= 4.02g favors SN2 reactions. In this experiment, the ease at which the product No. moles of 1-hexene = mass/molar mass= 4.02/84.16= 0.048 mols reacts with NaI in this test indicates that the product is a 1o alkyl halide. If 1 mole of 1-hexene produces 2-bromohexane . Hence, 1:1 ratio leads to 0.192 moles 2-bromohexane were collected, it being a 2o alkyl halide will take a much for 2-bromohexane. longer time to react because it is more hindered due to steric effects. Mass of 2-bromohexane = moles x molar mass = 0.048x 165.07= 7.92g (6.13A, 6.13 B, 6.13 C, Organic Chemistry, Solomons 10th ed). Mass percentage = (experimental / theoretical)x100% = ( 3.14/ 7.92)x100% = 39.63%

By Jason Lee

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Hypothesis:
1. If the distillate is collected from temperature of 80 oC and onwards during simple distillation of crude product, then the distillate will contain 2bromohexane. If the product contains 2bromohexane, then the time taken for a white precipitate to form in a AgNO3/EtOH Test done on the product will be less than 30 seconds*. If the product contains 2bromohexane, then the time taken for a white precipitate to form in a NaI/Acetone test done on the product will be more than 60 seconds*.

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*: Time range extracted from results of Exp 3:Reactivities of Alkyl halide done on 14/2/2014.