Title : PREPARATION OF n-BUTYL PHENYL ETHER BY SN2

REACTION
Objective : 1) To synthesize n-butyl phenyl ether through SN2 reaction
using sodium phenoxide and n-butyl bromide
2) To purify the crude product by distillation
3) To determine the boiling point of the n-butyl phenyl ether
Experimental :
44 mL of absolute ethanol has been poured into a 250 mL two necked round
bottom flask and also 3 boiling chips. After that, 1.91 g of sodium metal is put into the
flask and let the ethanol to react with the sodium.
The round bottom flask is put in the water bath as the reaction between the
ethanol and the sodium metal produce heat to make sure that the reflux occur
slowly.

After the reaction of sodium metal and ethanol finished, 7.3 mL of phenol in
10 mL of absolute ethanol is put into the flask and mixed thoroughly.

After about 1 minute, 13mL of n-butyl bromide is added through a dropper

funnel and the mixture is heated in water bath and left for reflux for 15 minutes. To
allow excess of ethanol to be distilled out.
 Then, 20 mL of water in pored into the cold reaction flask and then transferred
into separating funnel. The organic layer of the mixture is washed with 10% NaOH
solution two times with 5 mL. Then, the organic layer is further washed with 10%
H2SO4 solution followed by water. After separating the organic layer and the
aqueous layer, anhydrous MgSO4 is added to dry it. After that, the filtered organic
layer is poured into a pear shaped 25 mL and distilled using an air-bath.

Calculation of limiting reagent :

Equation 1
Volume of ethanol used : 44 mL
Density of ethanol : 0.7892 g/mL
Mass of ethanol used : (0.7892g/mL)/(44mL) = 34.72 g
Moles of ethanol : (34.72g)/(46.07g/mol) = 0.75 mol
Moles of sodium : (1.91g)/(22.99g/mol) = 0.08 mol
Based on the reaction equation,
1 mole of ethanol requires 1 mole of sodium
0.75 mole of ethanol requires 0.75 mole of sodium
Hence, the limiting reactant for this equation is sodium
0.08 mole of sodium will produce 0.08 mole of sodium ethoxide.
For next reaction,

Equation 2
Mass of phenol used : 7.8 g
Moles of phenol used : (7.8g)/(94.11g/mol) = 0.083 mol
Moles of sodium ethoxide used is 0.08 mol
Based on the reaction equation,
1 mole of CH3CH3ONa requires 1 mole of phenol
0.08 mole of CH3CH3ONa requires 0.08 mole of phenol
Hence, sodium ethoxide is the limiting reactant for this reaction.
0.08 mole of CH3CH3ONa will produce 0.08 mole sodium phenoxide

Equation 3
Mass of n-butyl bromide used : 16.52 g
Mole of n-butyl bromide : (16.52g)/(137.03g/mol) = 0.12 mol
Based on the above reaction equation,
1 mole of n-butyl bromide requires 1 mole of sodium phenoxide
0.08 mole of n-butyl bromide requires 0.08 mole of sodium phenoxide
Hence, n-butyl bromide is the limiting reactant for this reaction
0.08 mole of n-butyl bromide will produce 0.08 mole of n-butyl phenyl ether.

Theoretical yield of n-butyl phenyl ether :

0.08 mole of n-butyl phenyl ether will be produced.
Mass of n-butyl phenyl ether produced : (0.08mol) X (150.22g/mol) = 12.0176 g
Density of n-butyl phenyl ether : 0.93 g/mL
Expected volume of n-butyl phenyl ether : (12.0176g)/(0.93g/mL) = 13 mL
Results :
i) Mass of n-butyl phenyl ether (crude product) before air-bath distillation

Parameter Unit (g)

Mass of pear-shaped flask 32.69
Mass of pear-shaped flask + n-butyl phenyl ether (crude product) 36.71
Mass of n-butyl phenyl ether (crude product) 4.02

ii) Mass of n-butyl phenyl ether after air-bath distillation:

Parameter Unit (g)

Mass of pear-shaped flask 16.84
Mass of pear-shaped flask + n-butyl phenyl ether 20.15
Mass of n-butyl phenyl ether 3.31

Boiling point of n-butyl phenyl ether : 204oC

Volume of n-butyl phenyl ether : 3.71 mL
Density of n-butyl phenyl ether = (3.31g)/(3.71mL) = 0.89 g/mL

Percentage yield of n-butyl phenyl ether = (3.71mL)/(13mL) X 100% = 28.54%

Discussion :
For this experiment, alkyl halides is used to produce n-butyl phenyl ether which is n-
butyl bromide. Alkyl halides are very useful intermediates in organic synthesizes.
When putting the ethanol into the flask, the drying tube must put calcium chloride,
this is to avoid water vapour from coming inside the flask and react with the sodium
metal as the sodium metal is very reactive with water.
The reaction of sodium and ethanol is an exothermic reaction, the flask will become
very hot as time goes on. The hot flask must put into a water bath to cool it down a
little to let the mixture reflux slowly.
After the first distillation to remove ethanol, the mixture then transferred into the
separating funnel to separate the n-butyl phenyl ether and sodium bromide.
The organic layer which is n-butyl phenyl ether is washed with 10% NaOH, this is to
remove the acid phenol by neutralization process. After the washing process, the
aqueous solution is tested with red litmus to test whether there is still base in the
organic layer.
After that, the organic layer then washed with 10% H2SO4 to remove the excess
NaOH. Followed by water to remove the excess acid. Blue litmus paper is used to
check whether there is still any excess acid present.
Then, to make sure that the organic solution which is n-butyl phenyl ether is free
from water, MgSO4 is added. The organic solution is then filtered into the pear
shaped flask to remove the MgSO4 and to do the next distillation which is air bath
distillation to remove the excess ethanol that may be present.
Based on the results, the expected volume of the product of n-butyl phenyl ether is
13 mL, but the experimental result is 3.71 mL.
During the first air-bath distillation, the first drop temperature is 88oC and the highest
temperature of the distillation is at 204oC. The firsts drop temperature refer to the
boiling point of the ethanol and the highest temperature of the distillation refer to the
boiling point of the n-butyl phenyl ether.
Theoretically, the boiling point of ethanol is 78.37oC[1] and the boiling point of the n-
butyl phenyl ether is 210.3oC[2].
The wide range of the theory temperature and the experimental temperature maybe
cause by the error in handling the experiment. The recording for the temperature of
the first drop for the air bath distillation is taken a little bit later than the actual first
drop of the distillation, that’s why the recorded temperature is higher than the
theoretical value of the boiling point for ethanol.
As for the highest temperature which is differ for about 6 oC between the theoretical
and experimental result maybe because of the impurities that still present inside of
the organic solution during the air-bath distillation or maybe because the position of
the thermometer is a little bit higher than the suppose position, that’s why the
temperature is a little bit lower than the expected value.
During the addition of the sodium metal into the 44 mL absolute ethanol, there is
bubble gas formed. The gas released is the hydrogen gas. This can be seen from
the following equation.

Phenol is acidic and in acidic condition, the colour of the phenol is a little bit
yellowish. That’s why after the addition of phenol into the round bottom flask, the
colour of the mixture change from colourless to a light yellow.

Reaction mechanism :
Reaction of ethanol and Sodium metal:

+
H3C
O H + Na
H3C O
–
+
Na
H3C O Na

Reaction of Sodium phenoxide and n-butyl bromide:

–
O Na O H

+
+ Na + H3C
Br

O CH3
O CH3

– +
+ Br + Na
+ Na Br
Precaution step :
1) While handling the sodium metal, it must be completely dry and free from
water as the metal is very reactive with water that can cause explosion.
2) For chemical like phenol, they must be handled carefully as it is corrosive and
also phenol cannot be throw out into the sink as it is danger for aquatic
environment.
3) While recording the temperature during the distillation process, eye must be
perpendicular with the reading scale to avoid parallax error.
Conclusion :
n-butyl phenyl is synthesize through SN2 reaction using sodium phenoxide as
nucleophile and n-butyl bromide as substrate. The crude product is able to purify by
using the air-bath distillation. From the experiment, the boiling point of the n-butyl
phenyl ether is 204oC.
From the experiment, the conclusion that I got is that the thermometer must
be put on the right position during the distillation which is at the same level with the
mouth of the water condenser.
References :
[1] Helmenstine, Anne Marie, Ph.D. "Boiling Points of Ethanol, Methanol, and
Isopropyl Alcohol." ThoughtCo, May. 31, 2019, thoughtco.com/boiling-point-
of-alcohol-608491.
[2] National Center for Biotechnology Information. PubChem Database. Butyl phenyl
ether, CID=14311, https://pubchem.ncbi.nlm.nih.gov/compound/Butyl-phenyl-
ether (accessed on Oct. 13, 2019)
Post-lab questions :
1. Why must the excess alcohol be separated ?

The excess alcohol must be separated so that the boiling point that we got during the
air-bath distillation is the boiling point of the n-butyl phenyl ether. Also, when we
calculate the percentage yield of the product, we got the percentage for the final
product only and not including other substance too.

2. If (R)-2-bromobutane reacted with phenoxide ion through SN2 reaction, what will
be the expected product. State the stereochemistry of the compound. (Draw the
structure of the compound with the correct stereochemistry).

CH3

O H
CH3