EXPERIMENT 5 : THE PREPARATION OF 1-BROMOBUTANE FROM 1-BUTANOL

OBJECTIVE 1. To study the preparation of 1-bromobutane from 1-butanol by an SN2 reaction. 2. To study the method of purification of an organic compound by simple extraction.

INTRODUCTION In this experiment, the procedure to generate n-butyl ethyl ether from 1-butanol is divided into two parts. The first part involves the formation of n-butyl bromide from 1-butanol. Alkyl halides are very useful intermediates in organic syntheses. The most common synthetic preparation of alky halides is the replacement of the hydroxyl group, OH of an alcohol by a halogen, HX. The displacement of a hydroxyl group by halide ion is successful only in the presence of a strong acid. 1-butanol is used to be converted into 1-bromobutane with adding of sodium bromide and sulphuric acid. The nucleophile for the reaction is Br- ions. The nucleophile in this lab is generated from an aqueous solution of sodium bromide. The sulfuric acid acts as a catalyst in this reaction. The sulphuric acid protonates 1-butanol to produce suitable leaving group, OH, in SN2 reaction. The chemical reaction is shown as below:
CH3CH2CH2CH2OH + NaBr + H2SO4 CH3CH2CH2CH2-Br + NaHSO4 + H2O

If this displacement reaction is attempted in the absence of an acid it is unsuccessful because leaving group would be a hydroxide ion which is a poor leaving group and a strong base.

PROCEDURE 1. 17.0 g of sodium bromide was placed into the 100ml round bottom flask. 2. Followed by 17.0 ml of water. 3. The flask was swirled until the sodium bromide is dissolved. 4. Then, 10.0 ml of 1-butanol was added to the mixture. 5. The flask then placed in the ice bath. 6. 14 ml of concentrated sulfuric acid was poured into the flask little by little. 7. The flask was swirled gently. 8. The flask was assembled into a reflux apparatus. The mixture was reflux for 60 minutes.

9. The heat was turned off and the condensate was allowed to drain back into the flask. 10. After the reflux setup was cooled, the mixture was transferred into a separatory funnel and then the lower layer was discarded. 11. 14 ml of 9M H2SO4 was added to the funnel and the funnel was shook. 12. Again, discard the lower layer. 13. 14 ml of distilled water was added to the flask and shook the funnel. 14. The mixture was allowed to separate into two layers and drain the lower layer into a beaker. 15. The remaining aqueous layer was discarded. 16. The lower layer containing the product was transferred into an empty separatory funnel. 17. 14 ml of saturated sodium bicarbonate solution was added. 18. The flask was shook for one minute. And the lower layer was drained into an Erlenmeyer flask. 19. The product was dried with 1.0 g of anhydrous calcium chloride. The flask was swirled until clear solution obtained. 20. The 1-bromobutane was purified by simple distillation. 21. The clear, dry liquid was pipetted into a 50 ml round bottom flask. 22. Boiling chips were added and distillation started. 23. The collection of sample was started from 95OC until 101OC.

RESULTS 1-butanol MW (g/mol) Moles (mol) Grams (g) 74.1224 0.1093 8.1000 NaBr 102.8940 0.1656 17.0420 1-bromobutane 137.0191 0.1093 14.1645

The percentage yield = 94.58% Boiling point =

CALCULATION Weight of conical flask = 48.5742 g Weight of conical flask + weight of 1-bromobutane = 62.7387 g Weight of 1-bromobutane = 14.1645 g
CH3CH2CH2CH2OH + NaBr + H2SO4 CH3CH2CH2CH2-Br + NaHSO4 + H2O

Density = Mass = Number of mole of 1-butanol = = 0.1093 mol Number of mole of sodium bromide = = 0.1656 mol 1-butanol is the limiting reactant 1 mole of 1-butanol reacts with 1 mole of NaBr to produce 1 mole of 1-bromobutane. Thus, 0.1093 mole of 1-bromobutane is formed. Theoretical weight of 1-bromobutane = 0.1093 mole X 137.0191 g/mol = 14.97 g Actual weight of 1-bromobutane = 14.1645 g Yield percentage of 1-bromobutane = = x 100% x 100%

= 94.58%

DISCUSSION In the experiment, the primary alkyl halide 1-bromobutane can be prepared easily by allowing 1-butanol to react with sodium bromide and sulphuric acid. The sodium bromide reacts with sulphuric acid under reflux to produce hydrogen halides. The chemical reaction as shown in below indicates that the hydrogen halide is produced from the reaction. 2 NaBr + H2SO4 ------> 2 HBr + Na2SO4 The hydrogen halide produced is used to convert 1-butanol to become 1-bromobutane by undergoes nucleophilic substitution. Excess sulphuric acid serves to shift the equilibrium and thus to speed up the reaction by producing a higher concentration of hydrobromic acid. The sulphuric acid also protonates the hydroxyl group of 1-butanol so that water is displaced rather than the hydroxide ion OH-. The acid also protonates the water as it is produced in the reaction and deacticvates it(water) as a nucleophile, hence the water keeps the 1-bromobutane from being converted back into the alcohol by nucleophilic attack of water. Synthesis of 1-bromobutane from the 1-butanol is undergoes SN2 mechanism. SN2 is known as second order nucleophilic substitution for bimolecule. The essential feature of the SN2 mechanism is that take place in a single step without intermediates when the incoming nucleophile, hydrogen bromide reacts with the 1-butanol from a direction opposite the group that leaves. As the bromide ion, Br- comes in on one side and bonds to the carbon, the OH- departs from the other side, thereby inverting the stereochemical configuration. The mechanism is shown in the figure 1 as below.

Figure 1 Since the hydrogen halide is polar molecule, the bromide ion is partial negative and the hydrogen is partial positive. The highly partial negative bromide ion acts as a nucleophile to

attack the 1-butanol at the opposite side of the departing OH group. This leads to a transition state in which the new Br-C bond is partially forming at the same time the hold C-OH bond is partially breaking, in which the partial negative charge by both the incoming nucleophile and the leaving hydroxyl ions. The transition state for this inversion has the remaining three bonds to the carbon in a planar arrangement as shown in figure 1. The water is formed after the bromide successfully becomes part of the molecule. Sodium bicarbonate (mild acid) is added to neutralize the acidic solution. Anhydrous calcium chloride is added as drying agent to absorb water droplets in order to purify the organic layer. An excess drying agent should be used to ensure that all the water in solvent is removed. If the water remains in the materials collected, it could interfere with the analysis. After filter out the drying agent, several anti-bumping granules (boiling chips) are added to prevent over boiling during distillation. Distillation process is carried out to purify the 1-bromobutane in the range of temperature 90C to 105C. The pure 1-bromobutane is obtained in the distillation process.

QUESTION 1. The upper layer contained 1-bromobutane because the bottom layer, the aqueous layer a large percentage of H2SO4 and NaHSO4 which probably make the density of water higher than 1.00g/cm3.

2. densities : bromobutane = 1.2686 g/cm3 : sulfuric acid = 1.8g g/cm3 : water = 1.0 g/cm3

So at start the bromobutane is less dense than the sulfuric acid so forms a layer above the sulfuric acid. On a small scale the reaction is poured into a large volume of ice water and transferred to a separating funnel. The density of the aqueous phase is now close to 1.0 g/cm3 so the bromobutane is more dense and forms the lower layer. The aqueous phase is usually extracted several times with a solvent and the mixture separated by distillation.

3. The bicarbonate is used to wash the product because we want to remove the H2SO4 from the reaction.

4. The Anhydrous Calcium Chloride is added to dry 1-bromobutane by removing water. The solid should be filtered out to makes the distillation more efficient and less likely to create any complications. 5. SN2 mechanism :

CONCLUSION The preparation of 1-butanol from 1-bromobutane experienced SN2 mechanism and for this experiment, we succeed to yield about 95% of 1-bromobutane.

REFERENCES 1. http://myweb.brooklyn.liu.edu/swatson/Site/Laboratory_Manuals_files/Exp7.pdf 2. http://www.123helpme.com/view.asp?id=123090 3. http://1chemistry.blogspot.com/2011/05/preparation-of-n-butyl-ethyl-ether-from.html 4. http://www.napavalley.edu/people/sfawl/Documents/Chem%20240/Expt%2006%20%20Synthesis%20of%20t-Butyl%20Bromide.pdf